Nanocomposite Materials: Sustainable Environment

**107**

**Chapter 6**

**Abstract**

*Mousumi Sen*

**1. Introduction**

**2. Composites**

characteristics, some are as follows:

Nanocomposite Materials

Nanocomposites are the heterogeneous/hybrid materials that are produced by the mixtures of polymers with inorganic solids (clays to oxides) at the nanometric scale. Their structures are found to be more complicated than that of microcomposites. They are highly influenced by the structure, composition, interfacial interactions, and components of individual property. Most popularly, nanocomposites are prepared by the process within in situ growth and polymerization of biopolymer and inorganic matrix. With the rapid estimated demand of these striking potentially advanced materials, make them very much useful in various industries ranging from small scale to large to very large manufacturing units. With a great deal to mankind with environmental friendly, these offer advanced technologies in addition to the enhanced business opportunities to several industrial sectors like automobile, construction, electronics and electrical, food packaging, and technology transfer.

**Keywords:** nanocomposites, composites, phases, latex, disperse nanomaterials

These particles have different properties at their atomic level due to their size. This change in properties of nanoparticles is beneficial in many fields [1, 2]. Nanotechnology is one of the most interesting fields for researchers since the last century. Numbers of developments have been made since then in the field of nanotechnology. Nanoparticles can be classified as metal nanoparticles, nonmetal ceramic nanoparticles, semiconductor nanoparticles, and a well-known type is carbon nanoparticles [3]. Nanoparticles have those chemical and physical properties which makes them very different from that of the corresponding bulk materials due to their small size and large surface to volume ratio. They attract much attention because of their potential applications in many fields including

optics, electrics, magnetism, ceramics, and catalysis [4].

The nanoparticle includes the particles having size between 1 and 100 nm.

Composites are engineered or naturally occurring solid materials which results when two or more different constituent materials, each having its own significant characteristic (physical or chemical properties) are combined together to create a new substance with superior properties than original materials in a specific finished structure [5, 6]. They are commonly designed to offer wide range of properties and

## **Chapter 6** Nanocomposite Materials

*Mousumi Sen*

### **Abstract**

Nanocomposites are the heterogeneous/hybrid materials that are produced by the mixtures of polymers with inorganic solids (clays to oxides) at the nanometric scale. Their structures are found to be more complicated than that of microcomposites. They are highly influenced by the structure, composition, interfacial interactions, and components of individual property. Most popularly, nanocomposites are prepared by the process within in situ growth and polymerization of biopolymer and inorganic matrix. With the rapid estimated demand of these striking potentially advanced materials, make them very much useful in various industries ranging from small scale to large to very large manufacturing units. With a great deal to mankind with environmental friendly, these offer advanced technologies in addition to the enhanced business opportunities to several industrial sectors like automobile, construction, electronics and electrical, food packaging, and technology transfer.

**Keywords:** nanocomposites, composites, phases, latex, disperse nanomaterials

### **1. Introduction**

The nanoparticle includes the particles having size between 1 and 100 nm. These particles have different properties at their atomic level due to their size. This change in properties of nanoparticles is beneficial in many fields [1, 2]. Nanotechnology is one of the most interesting fields for researchers since the last century. Numbers of developments have been made since then in the field of nanotechnology. Nanoparticles can be classified as metal nanoparticles, nonmetal ceramic nanoparticles, semiconductor nanoparticles, and a well-known type is carbon nanoparticles [3]. Nanoparticles have those chemical and physical properties which makes them very different from that of the corresponding bulk materials due to their small size and large surface to volume ratio. They attract much attention because of their potential applications in many fields including optics, electrics, magnetism, ceramics, and catalysis [4].

### **2. Composites**

Composites are engineered or naturally occurring solid materials which results when two or more different constituent materials, each having its own significant characteristic (physical or chemical properties) are combined together to create a new substance with superior properties than original materials in a specific finished structure [5, 6]. They are commonly designed to offer wide range of properties and characteristics, some are as follows:


### **3. Nanocomposites**

Nanocomposites are those composites in which one phase has nanoscale morphology like nanoparticles, nanotubes, or lamellar nanostructure. They have multiphases, so are multiphasic materials, at least of the phases should have dimensions in the range of 10–100 nm. To overcome the limitation of different engineering materials now-adays, nanocomposites are emerged to provide beneficial alternatives. Nanocomposites can be classified on the basis of their dispersed matrix and dispersed phase materials [7]. With the help of this rapidly expanding field, now-a-days, it has been possible to generate many exciting new materials with novel properties via innovative synthetic approaches. The properties of the so-called found not only depended on the properties of their originals, but also crucially on their interfacial and morphological characteristics. Of course, we cannot ignore the fact that sometimes it also happened that the newly generated property in the material is unknown to the parent constituent materials [8, 9]. Hence, the idea behind nanocomposite is to use building blocks with dimensions in nanometer range to design and create new materials with unprecedented flexibility and improvement in their physical properties.

### **4. Advantages of designing novel nanocomposites**

Nanocomposites are the solid combination of а bulk matrix and nаnodimensionаl phase(s) which differ in properties due to dissimilarities in structure and chemistry. Properties that have indicated substantial improvements:


Among several nanocomposites, polymer-based nanomaterials are the most leading materials of current research and development. Characteristics like film

**109**

**Figure 1.**

*Nanocomposite Materials*

• Societal risks

*DOI: http://dx.doi.org/10.5772/intechopen.93047*

• Risk to health and environment

• Molecular manufacturing

derived polymers (**Figure 1**).

**5. Types of nanocomposites**

*Formation of nanocomposite materials.*

**5.1 Non-polymer-based nanocomposites**

*5.1.1 Metal-based nanocomposites*

of benefit to polymer-based nanocomposites [10].

• Formation of nanocomposite materials:

catalysts, and also in some high-value added materials [11].

presence or absence of polymeric material in the composite.

forming ability, activated functionalities, and dimensional variability provide lots

The potential risk of nanocomposites commonly occurs majorly in areas like

Nanocomposites can be formed by blending inorganic nanoclusters, fullerenes,

clays, metals, oxides, or semiconductors with numerous organic polymers or organic and organometallic compounds, biological molecules, enzymes, and sol-gel

Nanocomposite materials that are obtained by the combination of two or more separate building constituents in one material offers unique properties that plausibly arises from their small size, large surface area, and off course from the interfacial interaction between the phases. Their extra ordinary potential have been smoothly utilized to enhance the biological potential of many drugs, biomaterials,

Nanocomposite materials can be classified in the following way based on the

The nanocomposites in which the compositions do not contain any polymers or polymer-derived materials are called non-polymer-based nanocomposites (**Figure 2**). Non-polymer-based nanocomposites are also known as inorganic nanocomposites. They can be further classified into metal-based nanocomposites, ceramic-based nanocomposites, and ceramic-ceramic-based nanocomposites [12].

Bimetallic nanoparticles being investigated in detail in the form of either of alloy or core-shell structures due to their improved catalytic properties and advancement

### *Nanocomposite Materials DOI: http://dx.doi.org/10.5772/intechopen.93047*

forming ability, activated functionalities, and dimensional variability provide lots of benefit to polymer-based nanocomposites [10].

The potential risk of nanocomposites commonly occurs majorly in areas like


*Nanotechnology and the Environment*

• Stiffness and strength

• Low coefficient of expansion

• Ease in manufacturing complex shapes

flexibility and improvement in their physical properties.

• Hinders flame and reduce smoke generations

• Permeability of gases, water, and solvents are reduced

**4. Advantages of designing novel nanocomposites**

Nanocomposites are the solid combination of а bulk matrix and

nаnodimensionаl phase(s) which differ in properties due to dissimilarities in structure and chemistry. Properties that have indicated substantial improvements:

• Mechanical properties (strength, bulk modules, withstands limit, etc.)

• Enhance optical clarity as compared to conventionally filled polymers

Among several nanocomposites, polymer-based nanomaterials are the most leading materials of current research and development. Characteristics like film

Nanocomposites are those composites in which one phase has nanoscale morphology like nanoparticles, nanotubes, or lamellar nanostructure. They have multiphases, so are multiphasic materials, at least of the phases should have dimensions in the range of 10–100 nm. To overcome the limitation of different engineering materials now-adays, nanocomposites are emerged to provide beneficial alternatives. Nanocomposites can be classified on the basis of their dispersed matrix and dispersed phase materials [7]. With the help of this rapidly expanding field, now-a-days, it has been possible to generate many exciting new materials with novel properties via innovative synthetic approaches. The properties of the so-called found not only depended on the properties of their originals, but also crucially on their interfacial and morphological characteristics. Of course, we cannot ignore the fact that sometimes it also happened that the newly generated property in the material is unknown to the parent constituent materials [8, 9]. Hence, the idea behind nanocomposite is to use building blocks with dimensions in nanometer range to design and create new materials with unprecedented

• Simple repair of damaged structures

• Resistance аgаinst fatigue

• Resistance to corrosion

**3. Nanocomposites**

• Thermal stability

• More surface appearance

• Improved electrical conductivity

• Increased chemical resistance

**108**

• Formation of nanocomposite materials:

Nanocomposites can be formed by blending inorganic nanoclusters, fullerenes, clays, metals, oxides, or semiconductors with numerous organic polymers or organic and organometallic compounds, biological molecules, enzymes, and sol-gel derived polymers (**Figure 1**).

Nanocomposite materials that are obtained by the combination of two or more separate building constituents in one material offers unique properties that plausibly arises from their small size, large surface area, and off course from the interfacial interaction between the phases. Their extra ordinary potential have been smoothly utilized to enhance the biological potential of many drugs, biomaterials, catalysts, and also in some high-value added materials [11].

**Figure 1.** *Formation of nanocomposite materials.*

### **5. Types of nanocomposites**

Nanocomposite materials can be classified in the following way based on the presence or absence of polymeric material in the composite.

The nanocomposites in which the compositions do not contain any polymers or polymer-derived materials are called non-polymer-based nanocomposites (**Figure 2**). Non-polymer-based nanocomposites are also known as inorganic nanocomposites. They can be further classified into metal-based nanocomposites, ceramic-based nanocomposites, and ceramic-ceramic-based nanocomposites [12].

### **5.1 Non-polymer-based nanocomposites**

### *5.1.1 Metal-based nanocomposites*

Bimetallic nanoparticles being investigated in detail in the form of either of alloy or core-shell structures due to their improved catalytic properties and advancement

**Figure 2.** *Classification of polymer- and non-polymer-based nanocomposites.*

in optical properties related to individual and differentiate metals [13]. They can be characterized by:


Non-polymer-based nanocomposites can be also classified as: metal/metal nanocomposites, for example Pt-Ru nanocomposites.

### *5.1.2 Ceramic-based nanocomposites*

Ceramic-based nanocomposites are defined as ceramic composites with more than one solid phase, in which at least one of the phases has dimensions in the nanoscale range (<50–100 nm). In these types of composites, both the phases have combined magnetic, chemical, optical, and mechanical properties, for example hydroxyapatite/titania nanocomposites [14–16].

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*Nanocomposite Materials*

*DOI: http://dx.doi.org/10.5772/intechopen.93047*

*5.1.3 Ceramic-ceramic-based nanocomposites*

**6. Polymer-based nanocomposites**

nanocomposites (PNC) is almost same [19].

erties in the produced nanocomposites.

**6.1 Uses of polymer nanocomposites**

vinyl acetate are used in barrier applications.

The non-polymer-based nanocomposites can be also classified as ceramic/ceramic nanocomposites which can be used in the area of artificial joint implants for fracture failures and it could promptly reduce the cost of surgery and would extend the mobility of the patient. The life spam would increase by 30 years, if the use of zirconia-toughened alumina nanocomposite implants is used effectively. The other example of ceramic/ ceramic nanocomposites are calcium sulfate-biomimetic apatite nanocomposites [17]. The most promising prospects of both metal-based nanocomposites and ceramicbased nanocomposites are in the application of areas in dentistry in which the nonpolymer-based nanocomposites or the inorganic materials that is metal or ceramics such as calcium phosphate, hydroxyapatite, and bioactive glass nanoparticles are very advantageous in alveolar bone regeneration and enamel substitution [18].

The polymer or copolymer which contains nanoparticles or nanofillers dispersed in the polymer matrix is termed as poly nanocomposites. One dimension (1D) must be lying in the range of 1–50 nm and these possess several shapes like as platelets, fibers, spheroids, etc. Poly nanocomposites are in the category of multiphase systems such as, MPS namely composites, blends, and foams which can absorb about 95% of the production of plastics. So, these systems need controlled mixing, the achieved dispersion should be stable, dispersed phase should be oriented, and the compounding strategies which are involved for all MPS, which includes poly

Polymer nanocomposites are proposed as a class of materials with unique properties but, the most challenging property of PNCs is the complex interfacial areas in between the polymer matrices because of this small scale large specific area is created that highlight the importance of polymer-nanoparticle interactions. So, to achieve properties, such as, mechanical, thermal, optical, and electric, we need to analyze

Polymer nanocomposites are known to be a class of reinforced polymer with a very low, i.e., less than about 5% of nanometric clay particles. These substances gained huge attention simultaneously from both the academic institution as well as from industrial sectors commonly in the area of nanocomposites. This is actually due to their drastically enhanced or improved thermal, mechanical as well as the barrier properties as compared to the micro- and also the conventional composites. These materials can be differentiated notably by: improved fire resistance and thermal stability, improved barrier properties, and increased recyclability [21]. However, despite of having so many advantages, it is still very much difficult to prepare a uniform dispersion between the filler and the matrix, as shown in **Figure 3**. Hence, unlikely, it reflects the lower mechanical as well as thermal prop-

**Figure 4** shows the various uses of polymer nanocomposites irrespective of the nature of the field used. By the hydrolysis of tetraethyl-ortho-silicate, the hybrids made of poly rubber (dimethyl siloxane) and nanosilica can be given a specific shape like objects, such as golf balls (**Figure 5**). Many number of polymer nanocomposites for example, rubber, propylene, styrene butadiene rubber, and ethylene

the intercalation process among the nanoparticles and polymer bases [20].

These can be characterized by:


*Nanotechnology and the Environment*

characterized by:

**Figure 2.**

• Super plasticity,

• Lower melting points,

• Increased strength and hardness,

*Classification of polymer- and non-polymer-based nanocomposites.*

• Improved magnetic properties,

*5.1.2 Ceramic-based nanocomposites*

These can be characterized by:

• Increased strength and hardness

• Better toughness

• Increased ductility

• Increased electrical resistivity, etc.

nanocomposites, for example Pt-Ru nanocomposites.

hydroxyapatite/titania nanocomposites [14–16].

in optical properties related to individual and differentiate metals [13]. They can be

Non-polymer-based nanocomposites can be also classified as: metal/metal

Ceramic-based nanocomposites are defined as ceramic composites with more than one solid phase, in which at least one of the phases has dimensions in the nanoscale range (<50–100 nm). In these types of composites, both the phases have combined magnetic, chemical, optical, and mechanical properties, for example

**110**

### *5.1.3 Ceramic-ceramic-based nanocomposites*

The non-polymer-based nanocomposites can be also classified as ceramic/ceramic nanocomposites which can be used in the area of artificial joint implants for fracture failures and it could promptly reduce the cost of surgery and would extend the mobility of the patient. The life spam would increase by 30 years, if the use of zirconia-toughened alumina nanocomposite implants is used effectively. The other example of ceramic/ ceramic nanocomposites are calcium sulfate-biomimetic apatite nanocomposites [17].

The most promising prospects of both metal-based nanocomposites and ceramicbased nanocomposites are in the application of areas in dentistry in which the nonpolymer-based nanocomposites or the inorganic materials that is metal or ceramics such as calcium phosphate, hydroxyapatite, and bioactive glass nanoparticles are very advantageous in alveolar bone regeneration and enamel substitution [18].

### **6. Polymer-based nanocomposites**

The polymer or copolymer which contains nanoparticles or nanofillers dispersed in the polymer matrix is termed as poly nanocomposites. One dimension (1D) must be lying in the range of 1–50 nm and these possess several shapes like as platelets, fibers, spheroids, etc. Poly nanocomposites are in the category of multiphase systems such as, MPS namely composites, blends, and foams which can absorb about 95% of the production of plastics. So, these systems need controlled mixing, the achieved dispersion should be stable, dispersed phase should be oriented, and the compounding strategies which are involved for all MPS, which includes poly nanocomposites (PNC) is almost same [19].

Polymer nanocomposites are proposed as a class of materials with unique properties but, the most challenging property of PNCs is the complex interfacial areas in between the polymer matrices because of this small scale large specific area is created that highlight the importance of polymer-nanoparticle interactions. So, to achieve properties, such as, mechanical, thermal, optical, and electric, we need to analyze the intercalation process among the nanoparticles and polymer bases [20].

Polymer nanocomposites are known to be a class of reinforced polymer with a very low, i.e., less than about 5% of nanometric clay particles. These substances gained huge attention simultaneously from both the academic institution as well as from industrial sectors commonly in the area of nanocomposites. This is actually due to their drastically enhanced or improved thermal, mechanical as well as the barrier properties as compared to the micro- and also the conventional composites. These materials can be differentiated notably by: improved fire resistance and thermal stability, improved barrier properties, and increased recyclability [21].

However, despite of having so many advantages, it is still very much difficult to prepare a uniform dispersion between the filler and the matrix, as shown in **Figure 3**. Hence, unlikely, it reflects the lower mechanical as well as thermal properties in the produced nanocomposites.

### **6.1 Uses of polymer nanocomposites**

**Figure 4** shows the various uses of polymer nanocomposites irrespective of the nature of the field used. By the hydrolysis of tetraethyl-ortho-silicate, the hybrids made of poly rubber (dimethyl siloxane) and nanosilica can be given a specific shape like objects, such as golf balls (**Figure 5**). Many number of polymer nanocomposites for example, rubber, propylene, styrene butadiene rubber, and ethylene vinyl acetate are used in barrier applications.

**Figure 3.**

*Uniform dispersion between the filler and matrix in nanocomposites.*

### **Figure 4.**

*Various uses of polymer nanocomposites.*

**Figure 5.** *Rubbery hybrids with different shapes.*

They can act as a tremendous barrier for chemicals like toluene, sulfuric acid, and hydrochloric acid as well as for several gases such as, carbon dioxide, oxygen, and nitrogen [22, 23]. They are also utilized in chemical protective and surgical gloves as they have excellent solvent barrier properties in order for avoiding contamination from medicine.

Polymer nanocomposites are also used in food packaging, and the particular examples for food packaging includes processed cheese, meat, and dairy products also the medical containers for carrying blood collection tubes, baby pacifiers, and drinking water bottles. To enhance the barrier, mechanical properties and the life of the product clay-based polymer nanocomposites are been used in plastic bottles [24].

**113**

*Nanocomposite Materials*

**Figure 6.**

*DOI: http://dx.doi.org/10.5772/intechopen.93047*

Nanocomposites are also incorporated for beer bottle manufacture, so as to reduce many problems like biological and non-biological aspects, beer colloids instability, oxygen permeation, and change in taste due to light exposure. The double core Wilson tennis ball is the most recently commercialized sports goods (**Figure 6**), in which the coating of clay nanocomposites is done in order to maintain the internal pressure for a long period of time and also the core is coated by butyl rubber clay

In today's time, the biggest milestone is the incorporation or application of polymer/ clay nanocomposites in the field of electronics and automobile sectors. Specifically to decrease the solvent transmission through polymers like elastomers, poly urethane, is the most impressive ability nanoclay incorporation. The poly nanocomposites help in the reduction of weight and processing cost so that they used by tire companies which are the major driving force for their usage. It is the naturally obtained materials which possesses low density. When the clay incorporated tires are compared with the ordinary ones then it is found that they have excellent mechanical properties and also improved gas barrier performance for tubeless tires uses [25]. Mostly for automobile tire manufacturing, styrene butadiene and natural rubber nanocomposites are preferred the most. It is due to their improved thermal properties and abrasion resistance that contribute to the long life of the tires. They have great applications in solar cells, transistors, battery

The most important modifying property of surfaces is coating. So, many methods and strategies are tried by the researchers to improve the surface properties of several products. The properties such as, excellent resistance for chemicals, better barrier properties, super hydrophobicity, and corrosion resistance are exhibited by nanoclay incorporated thermoset polymer nanocoatings [18]. The process parameters, such as dipping time, nature of surfactant, temperature, etc., determine the coating thickness. The thermoset polymer nanocoatings which are incorporated clay and nanosilver could improve the antibacterial properties and is used in medical sectors.

The name "Bi-nanocomposites" is given as they are characterized as natural nanocomposite. To understand their essential roles in biological systems, their structures and properties are studied by biologists. Bio-nanocomposites are

nanocomposite which doubled the shell life and acts a gas barrier.

*The core of this Wilson tennis ball is covered by a polymer-clay nanocomposite coating.*

**6.2 Electronics and automobile sectors**

manufacturing, etc.

**6.4 Bio-nanocomposites**

**6.3 Coatings**

*Nanotechnology and the Environment*

*Uniform dispersion between the filler and matrix in nanocomposites.*

**112**

**Figure 4.**

**Figure 3.**

**Figure 5.**

tamination from medicine.

*Rubbery hybrids with different shapes.*

*Various uses of polymer nanocomposites.*

They can act as a tremendous barrier for chemicals like toluene, sulfuric acid, and hydrochloric acid as well as for several gases such as, carbon dioxide, oxygen, and nitrogen [22, 23]. They are also utilized in chemical protective and surgical gloves as they have excellent solvent barrier properties in order for avoiding con-

Polymer nanocomposites are also used in food packaging, and the particular examples for food packaging includes processed cheese, meat, and dairy products also the medical containers for carrying blood collection tubes, baby pacifiers, and drinking water bottles. To enhance the barrier, mechanical properties and the life of the product clay-based polymer nanocomposites are been used in plastic bottles [24].

**Figure 6.** *The core of this Wilson tennis ball is covered by a polymer-clay nanocomposite coating.*

Nanocomposites are also incorporated for beer bottle manufacture, so as to reduce many problems like biological and non-biological aspects, beer colloids instability, oxygen permeation, and change in taste due to light exposure. The double core Wilson tennis ball is the most recently commercialized sports goods (**Figure 6**), in which the coating of clay nanocomposites is done in order to maintain the internal pressure for a long period of time and also the core is coated by butyl rubber clay nanocomposite which doubled the shell life and acts a gas barrier.

### **6.2 Electronics and automobile sectors**

In today's time, the biggest milestone is the incorporation or application of polymer/ clay nanocomposites in the field of electronics and automobile sectors. Specifically to decrease the solvent transmission through polymers like elastomers, poly urethane, is the most impressive ability nanoclay incorporation. The poly nanocomposites help in the reduction of weight and processing cost so that they used by tire companies which are the major driving force for their usage. It is the naturally obtained materials which possesses low density. When the clay incorporated tires are compared with the ordinary ones then it is found that they have excellent mechanical properties and also improved gas barrier performance for tubeless tires uses [25]. Mostly for automobile tire manufacturing, styrene butadiene and natural rubber nanocomposites are preferred the most. It is due to their improved thermal properties and abrasion resistance that contribute to the long life of the tires. They have great applications in solar cells, transistors, battery manufacturing, etc.

### **6.3 Coatings**

The most important modifying property of surfaces is coating. So, many methods and strategies are tried by the researchers to improve the surface properties of several products. The properties such as, excellent resistance for chemicals, better barrier properties, super hydrophobicity, and corrosion resistance are exhibited by nanoclay incorporated thermoset polymer nanocoatings [18]. The process parameters, such as dipping time, nature of surfactant, temperature, etc., determine the coating thickness. The thermoset polymer nanocoatings which are incorporated clay and nanosilver could improve the antibacterial properties and is used in medical sectors.

### **6.4 Bio-nanocomposites**

The name "Bi-nanocomposites" is given as they are characterized as natural nanocomposite. To understand their essential roles in biological systems, their structures and properties are studied by biologists. Bio-nanocomposites are

designed originally and are present to fulfill the needs of life and to meet surrounding environmental conditions so they can guarantee the living of the associated species. Natural materials are different in terms of structure and compositions but the design of bio-nanocomposites require biological molecules to consider them as synthetic building blocks, which is far more distant from the context of their own natural function. They are made of biopolymers and inorganic solids which has the dimension in the range of 1–100 nm. Due to their multidimensional properties such as antimicrobial activity, biocompatibility, and biodegradability they have several numbers of applications. The effective outcome of growing needs of bio-based polymers is the drastic reduction in the usage of fossil fuels. Bio-nanocomposites have easily replaced conventional non-biodegradable petroleum-based plastic as they are light weight and eco-friendly; they have become a sustainable that is future lasting material for use in high performance applications. As they are biocompatible, it makes them beneficial for biomedical applications and also makes them suitable for cosmetics and biotechnology applications. They have dominant significance in the future as green sustainable materials [26]. Bio-nanocomposites will act as substituents for the currently used petroleum-based polymers.

### **7. Uses of bio-nanocomposites**


### **8. Applications of nanocomposites**

Nanocomposites have been growing with a speedy rate so as their large number of applications. In the next 10 years, the worldwide production will exceed 600,000 tons in the following regions:

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**Acknowledgements**

*Nanocomposite Materials*

**9. Future aspects**

**10. Conclusion**

*DOI: http://dx.doi.org/10.5772/intechopen.93047*

5.Anti-corrosion barrier coatings

mower hood, covers for mobile phones, etc.

Nanocomposites have also attracted the field of automotive and industrial applications by doing enhancements in especially the mechanical properties. They can be used or applied in the various vehicles types like engine covers, door covers, and timing belt covers. Other applications are usage as blades for vacuum cleaners,

Modification of surface properties of nanoparticles by treating them with green agents for specific applications having specific improved microstructural properties

Advance optimization of the polymerization conditions during the preparation

Detailed study on the effect of composition of the nanocomposites to build up

Preparation of nanocomposites as well as their blends by using the materials like polymer blends along with the melt blending technologies. Hence, the advantages of the properties of the individual material as well as their coaction can be developed. Using nanocomposites to make flexible batteries: "А nanocomposite of cellulous

With the rapid development of nanotechnology in the past few years, the study of the nanocomposites has been increasingly become important in the development of new materials for advanced applications. To fulfill the growing needs of multifunctional materials, nanocomposites are the right choice as these are not only the versatile class of materials, but also have a high level of integrated association. It is a multidisciplinary field which includes the knowledge of scientific background as well as technological aspects to create macroscopic engineered materials obtained through nanolevel structures. These materials are suitable materials to meet the emerging demands arising from scientific and technologic advances. Outstanding potentials of nanocomposites can be exemplified by the massive investments from many companies and governments throughout the world. As a result, nanocomposites are expected to generate a great impact in world economy and business. The important aspects is that it provides plausible benefit to many of our industrial sector like electronics and electrical industry, chemical industry, transportation sectors, health care organizations, and above an all the protection of the environment. Hence, these are expected to have high impact on

making the environment cleaner, greener, and safer in the coming years.

encouragement to complete the above assessment.

The author is very much thankful to the faculty members of AIAS, Amity University, Uttar Pradesh for providing necessary facilities and their constant

materials and nanotubes could be used to make а conductive paper. When this conductive paper is soaked in an electrolyte, а flexible battery is formed."

like improved exfoliation, compatibility, and also thermal stability.

the developed microstructures during the preparation activities.

of the nanocomposites in order to get maximum output with minimal cost.

6.Lubricant and stretch paints


Nanocomposites have also attracted the field of automotive and industrial applications by doing enhancements in especially the mechanical properties. They can be used or applied in the various vehicles types like engine covers, door covers, and timing belt covers. Other applications are usage as blades for vacuum cleaners, mower hood, covers for mobile phones, etc.

### **9. Future aspects**

*Nanotechnology and the Environment*

**7. Uses of bio-nanocomposites**

based nanocomposite is applicable.

**8. Applications of nanocomposites**

1.Superior strength fibers and films

tons in the following regions:

2.UV protection gels

3.Drug delivery systems

4.New fire retardant materials

of bioinorganic composite materials is done.

ing of compostable bags as they are eco-friendly.

membranes.

designed originally and are present to fulfill the needs of life and to meet surrounding environmental conditions so they can guarantee the living of the associated species. Natural materials are different in terms of structure and compositions but the design of bio-nanocomposites require biological molecules to consider them as synthetic building blocks, which is far more distant from the context of their own natural function. They are made of biopolymers and inorganic solids which has the dimension in the range of 1–100 nm. Due to their multidimensional properties such as antimicrobial activity, biocompatibility, and biodegradability they have several numbers of applications. The effective outcome of growing needs of bio-based polymers is the drastic reduction in the usage of fossil fuels. Bio-nanocomposites have easily replaced conventional non-biodegradable petroleum-based plastic as they are light weight and eco-friendly; they have become a sustainable that is future lasting material for use in high performance applications. As they are biocompatible, it makes them beneficial for biomedical applications and also makes them suitable for cosmetics and biotechnology applications. They have dominant significance in the future as green sustainable materials [26]. Bio-nanocomposites will act as

1.Bio-nanocomposites are used in cosmetics industries and also in the fabrica-

2.They are also very beneficial as catalysts, contact lenses, and gas-separation

3.In the treatment of osteomyelitis, by the regeneration of tissue biopolymer-

4.Artificial bone implants involves nanostructured organic/inorganic nanocom-

5.Using live cells of functionalized particles, controlled electrophoretic assembly

6.They are largely applicable in diagnostic, drug delivery, and tissue generation.

7.In industries, they are used as actuators. They are also used in the manufactur-

Nanocomposites have been growing with a speedy rate so as their large number of applications. In the next 10 years, the worldwide production will exceed 600,000

tion of implants, scaffolds, diagnostics, and biomedical devices.

posites which are useful in managing load-bearing bone grafts.

substituents for the currently used petroleum-based polymers.

**114**

Modification of surface properties of nanoparticles by treating them with green agents for specific applications having specific improved microstructural properties like improved exfoliation, compatibility, and also thermal stability.

Advance optimization of the polymerization conditions during the preparation of the nanocomposites in order to get maximum output with minimal cost.

Detailed study on the effect of composition of the nanocomposites to build up the developed microstructures during the preparation activities.

Preparation of nanocomposites as well as their blends by using the materials like polymer blends along with the melt blending technologies. Hence, the advantages of the properties of the individual material as well as their coaction can be developed.

Using nanocomposites to make flexible batteries: "А nanocomposite of cellulous materials and nanotubes could be used to make а conductive paper. When this conductive paper is soaked in an electrolyte, а flexible battery is formed."

### **10. Conclusion**

With the rapid development of nanotechnology in the past few years, the study of the nanocomposites has been increasingly become important in the development of new materials for advanced applications. To fulfill the growing needs of multifunctional materials, nanocomposites are the right choice as these are not only the versatile class of materials, but also have a high level of integrated association. It is a multidisciplinary field which includes the knowledge of scientific background as well as technological aspects to create macroscopic engineered materials obtained through nanolevel structures. These materials are suitable materials to meet the emerging demands arising from scientific and technologic advances. Outstanding potentials of nanocomposites can be exemplified by the massive investments from many companies and governments throughout the world. As a result, nanocomposites are expected to generate a great impact in world economy and business. The important aspects is that it provides plausible benefit to many of our industrial sector like electronics and electrical industry, chemical industry, transportation sectors, health care organizations, and above an all the protection of the environment. Hence, these are expected to have high impact on making the environment cleaner, greener, and safer in the coming years.

### **Acknowledgements**

The author is very much thankful to the faculty members of AIAS, Amity University, Uttar Pradesh for providing necessary facilities and their constant encouragement to complete the above assessment.

*Nanotechnology and the Environment*

### **Author details**

Mousumi Sen Amity Institute of Applied Sciences, Amity University, Noida, Uttar Pradesh, India

\*Address all correspondence to: mosumi1976@gmail.com

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

**117**

*Nanocomposite Materials*

**References**

*DOI: http://dx.doi.org/10.5772/intechopen.93047*

[1] Yang C, Li W, Yang Z, Gu L, Yu Y. Nanoconfined antimony in sulfur and nitrogen co-doped three-dimensionally (3D) interconnected macroporous carbon for high performance sodium-ion batteries. Nano Energy. 2015;**18**:12-19

studies. Journal of Alloys and Compounds. 2010;**500**:87-92

[10] Al-Johani H, Abdel Salam M. Kinetics and thermodynamic study of aniline adsorption by multi-walled carbon nanotubes from aqueous solution. Journal of Colloid and Interface Science. 2011;**360**:760-767

[11] Xin X, Wei Q, Yang J, Yan L, Feng R, Chen G, et al. Highly efficient removal of heavy metal ions by

Journal. 2012;**184**:132-140

2011;**10**:2572-2578

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1992;**1**:1-19

2004

[12] Khandoker N, Hawkins SC, Ibrahim R, Huynh CP, Deng F. Tensile strength of spinnable multiwall carbon nanotubes. Procedia Engineering.

aminefunctionalized mesoporous Fe3O4 nanoparticles. Chemical Engineering

[13] Fam DWH, Palaniappan A, Tok AIY, Liedberg B, Moochhala SM. A review on technological aspects influencing commercialization of carbon nanotube

[14] Gleiter H. Materials with ultrafine microstructures: Retrospectives and perspectives. Nanostructured Materials.

[15] Braun T, Schubert A, Sindelys Z. Nanoscience and nanotechnology on the balance. Scientometrics. 1997;**38**:321-325

[16] Pandey JK, Kumar AP, Misra M, Mohanty AK, Drzal LT, Singh RP. Recent

[17] Thostenson ET, Li C, Chou TW. Nanocomposites in context. Composites

[18] Vaia RA, Wagner HD. Framework for nanocomposites. Materials Today.

nanocomposites. Journal of Nanoscience

advances in biodegradable

and Nanotechnology. 2005

Science and Technology. 2005

[2] Pan D, Wang S, Zhao B, Wu M, Zhang H, Wang Y, et al. Li storage properties of disordered graphene nanosheets. Chemistry of Materials.

Engelhard M, Chen X, Nie Z, et al. Sodium ion insertion in hollow carbon nanowires for battery applications. Nano Letters. 2013;**13**:3909-3914

[4] Kaskhedikar NA, Maier J. Lithium storage in carbon nanostructures. Advanced Materials. 2010;**21**:2664-2680

[5] Shin WH, Jeong HM, Kim BG, Kang JK, Choi JW. Nitrogen-doped multiwall carbon nanotubes for lithium storage with extremely high capacity. Nano Letters. 2012;**12**:2283-2288

[6] Liu X, Antonietti M. Molten salt activation for synthesis of porous carbon nanostructures and carbon sheets. Carbon. 2014;**69**:460-466

[7] Wang J, Kaskel S. KOH activation of carbon-based materials for energy storage. Journal of Materials Chemistry.

[8] Wang S, Xiao C, Xing Y, Xu H, Zhang S. Carbon nanofibers/nanosheets hybrid derived from cornstalks as a sustainable anode for Li-ion batteries. Journal of Materials Chemistry A.

[9] Abdel Salam M, Mokhtar M, Basahel SN, Al Thabaiti SA, Obaid AY. Removal of chlorophenol from aqueous solution by multi-walled carbon

nanotubes: Kinetic and thermodynamic

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2009;**21**:3136-3142

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*Nanocomposite Materials DOI: http://dx.doi.org/10.5772/intechopen.93047*

### **References**

*Nanotechnology and the Environment*

**116**

**Author details**

Amity Institute of Applied Sciences, Amity University, Noida, Uttar Pradesh, India

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

\*Address all correspondence to: mosumi1976@gmail.com

provided the original work is properly cited.

Mousumi Sen

[1] Yang C, Li W, Yang Z, Gu L, Yu Y. Nanoconfined antimony in sulfur and nitrogen co-doped three-dimensionally (3D) interconnected macroporous carbon for high performance sodium-ion batteries. Nano Energy. 2015;**18**:12-19

[2] Pan D, Wang S, Zhao B, Wu M, Zhang H, Wang Y, et al. Li storage properties of disordered graphene nanosheets. Chemistry of Materials. 2009;**21**:3136-3142

[3] Shao Y, Xiao J, Wang W, Engelhard M, Chen X, Nie Z, et al. Sodium ion insertion in hollow carbon nanowires for battery applications. Nano Letters. 2013;**13**:3909-3914

[4] Kaskhedikar NA, Maier J. Lithium storage in carbon nanostructures. Advanced Materials. 2010;**21**:2664-2680

[5] Shin WH, Jeong HM, Kim BG, Kang JK, Choi JW. Nitrogen-doped multiwall carbon nanotubes for lithium storage with extremely high capacity. Nano Letters. 2012;**12**:2283-2288

[6] Liu X, Antonietti M. Molten salt activation for synthesis of porous carbon nanostructures and carbon sheets. Carbon. 2014;**69**:460-466

[7] Wang J, Kaskel S. KOH activation of carbon-based materials for energy storage. Journal of Materials Chemistry. 2012;**22**:3710-23725

[8] Wang S, Xiao C, Xing Y, Xu H, Zhang S. Carbon nanofibers/nanosheets hybrid derived from cornstalks as a sustainable anode for Li-ion batteries. Journal of Materials Chemistry A. 2015;**3**:6742-6746

[9] Abdel Salam M, Mokhtar M, Basahel SN, Al Thabaiti SA, Obaid AY. Removal of chlorophenol from aqueous solution by multi-walled carbon nanotubes: Kinetic and thermodynamic studies. Journal of Alloys and Compounds. 2010;**500**:87-92

[10] Al-Johani H, Abdel Salam M. Kinetics and thermodynamic study of aniline adsorption by multi-walled carbon nanotubes from aqueous solution. Journal of Colloid and Interface Science. 2011;**360**:760-767

[11] Xin X, Wei Q, Yang J, Yan L, Feng R, Chen G, et al. Highly efficient removal of heavy metal ions by aminefunctionalized mesoporous Fe3O4 nanoparticles. Chemical Engineering Journal. 2012;**184**:132-140

[12] Khandoker N, Hawkins SC, Ibrahim R, Huynh CP, Deng F. Tensile strength of spinnable multiwall carbon nanotubes. Procedia Engineering. 2011;**10**:2572-2578

[13] Fam DWH, Palaniappan A, Tok AIY, Liedberg B, Moochhala SM. A review on technological aspects influencing commercialization of carbon nanotube sensors. 2011;**157**:1-7

[14] Gleiter H. Materials with ultrafine microstructures: Retrospectives and perspectives. Nanostructured Materials. 1992;**1**:1-19

[15] Braun T, Schubert A, Sindelys Z. Nanoscience and nanotechnology on the balance. Scientometrics. 1997;**38**:321-325

[16] Pandey JK, Kumar AP, Misra M, Mohanty AK, Drzal LT, Singh RP. Recent advances in biodegradable nanocomposites. Journal of Nanoscience and Nanotechnology. 2005

[17] Thostenson ET, Li C, Chou TW. Nanocomposites in context. Composites Science and Technology. 2005

[18] Vaia RA, Wagner HD. Framework for nanocomposites. Materials Today. 2004

[19] Fischer H. Polymer nanocomposites: From fundamental research to specific applications. Materials Science and Engineering. 2003

[20] Nalwa HS. Handbook of Nanostructured Materials and Technology. New York: Academic Press; 2000

[21] Ray SS, Bousmina M. Biodegradable polymers and their layered silicate nanocomposites: In greening the 21st century materials world. Progress in Materials Science. 2005;**50**:962

[22] Stankovich S, et al. Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium 4-styrenesulfonate). Journal of Materials Chemistry. 2006;**16**:155-158

[23] Qiuli Z, Zhenjiang J, Jun Z, Xicheng Z, Xinzhe L. Preparation of lanthanum oxide nanoparticles by chemical precipitation method. Materials Science Forum. 2012;**724**:233-236

[24] Basak Y, Kokuoz K, Serivalsatit BK, Olt G, McCormick E, John B. Er-doped Y2O3 nanoparticles: A comparison of different synthesis methods. Journal of the American Ceramic Society. 2009

[25] Mirosław Z, Kepinski L, Forget S, Chénais S. Preparation and Characterization of Lanthanum Oxide doped Barium Zirconate Titanate (BaZr0.1Ti0.9O3; BZT) Ferroelectric Glass Ceramics. Springer Series in Optical Sciences. p. 175. DOI: 10.1007/978-3-642-36705-2\_2

[26] Higgins TV. Improved optical properties in nanocrystalline Ce:YGG garnets via normal and reverse strike co-precipitation method. The Three Phases of Lasers: Solid-State, Gas, and Liquid. Laser Focus World. July 1995. pp. 73-85

**119**

in various crops.

**Chapter 7**

**Abstract**

**1. Introduction**

Novel Slow Release

*Muthuraman Yuvaraj and* 

Nanocomposite Fertilizers

**Keywords:** nanofertilizer, slow release, composite, use efficiency

Nanotechnology deals with atom-by-atom manipulation and the strategies and products developed are quite precise. Despite the fact that the nanotechnology is noticeably exploited in the subject of energy, environment and health, the research is agricultural sciences had just scratched the surface. However, the potentials of nanotechnology in agricultural sciences had been reviewed. Among the applications, nanofertilizers technology is very revolutionary and known to exhibit

economic advantage if the products advanced are economically feasible and socially sustainable. These nano fertilizers are pronounced to reduce nutrient loss due to leaching, emissions, and long-term incorporation by soil microorganisms.

Today agriculture in the world is facing major tasks are reduction in yield, shrinking in the cultivable land due to globalization, less efficiency of nutrient, lack of nutrient availability and uptake is poor in soil, decreasing organic matter in soil, deficiency of water accessibility. In this critical situation it is more challenging to produce adequate food to feed the increasing populaces, which is projected to pass 9 billion by 2050. The nanofertilizer is ecologically safe and increase soil fertility, crop productivity and nutrient use efficacy. Nanofertilizer deals with atom-by-atom manipulation and the processes and products evolved are quite precise. Despite the fact that the nanotechnology is greatly exploited in the field of energy, environment and health, the research is agricultural sciences had just scratched the surface. Conversely, the importance and potentials of nanotechnology in agricultural sciences had been reviewed [1]. The nanofertilizers technology is very inventive and known to show economic benefit if the products evolved are economically viable and socially maintainable. These customized nanofertilizers are reported to

decrease nutrient loss due to leaching, emissions in soil ecosystem [2].

Nano based encapsulated and slow release fertilizers increase the uptake of nutrients, enhance fertility of soil and decreasing toxic effects associated with over application of fertilizer. In Tamil Nadu Agricultural University, Coimbatore, various nano-zeolite based fertilizer research carried out with Nitrogen [3, 4], phosphorous [5], potassium [6], sulfur [7, 8] have been synthesized, characterized and examined

*Kizhaeral Sevathapandian Subramanian*

### **Chapter 7**

*Nanotechnology and the Environment*

[20] Nalwa HS. Handbook of Nanostructured Materials and

Engineering. 2003

2000

[19] Fischer H. Polymer nanocomposites: From fundamental research to specific applications. Materials Science and

Technology. New York: Academic Press;

[21] Ray SS, Bousmina M. Biodegradable polymers and their layered silicate nanocomposites: In greening the 21st century materials world. Progress in Materials Science. 2005;**50**:962

[22] Stankovich S, et al. Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium 4-styrenesulfonate). Journal of Materials Chemistry. 2006;**16**:155-158

[23] Qiuli Z, Zhenjiang J, Jun Z, Xicheng Z, Xinzhe L. Preparation of lanthanum oxide nanoparticles by chemical precipitation method. Materials Science Forum.

[25] Mirosław Z, Kepinski L,

Forget S, Chénais S. Preparation and Characterization of Lanthanum Oxide doped Barium Zirconate Titanate (BaZr0.1Ti0.9O3; BZT) Ferroelectric Glass Ceramics. Springer Series in Optical Sciences. p. 175. DOI: 10.1007/978-3-642-36705-2\_2

[26] Higgins TV. Improved optical properties in nanocrystalline Ce:YGG garnets via normal and reverse strike co-precipitation method. The Three Phases of Lasers: Solid-State, Gas, and Liquid. Laser Focus World. July 1995.

[24] Basak Y, Kokuoz K, Serivalsatit BK, Olt G, McCormick E, John B. Er-doped Y2O3 nanoparticles: A comparison of different synthesis methods. Journal of the American Ceramic Society. 2009

2012;**724**:233-236

**118**

pp. 73-85

## Novel Slow Release Nanocomposite Fertilizers

*Muthuraman Yuvaraj and Kizhaeral Sevathapandian Subramanian*

### **Abstract**

Nanotechnology deals with atom-by-atom manipulation and the strategies and products developed are quite precise. Despite the fact that the nanotechnology is noticeably exploited in the subject of energy, environment and health, the research is agricultural sciences had just scratched the surface. However, the potentials of nanotechnology in agricultural sciences had been reviewed. Among the applications, nanofertilizers technology is very revolutionary and known to exhibit economic advantage if the products advanced are economically feasible and socially sustainable. These nano fertilizers are pronounced to reduce nutrient loss due to leaching, emissions, and long-term incorporation by soil microorganisms.

**Keywords:** nanofertilizer, slow release, composite, use efficiency

### **1. Introduction**

Today agriculture in the world is facing major tasks are reduction in yield, shrinking in the cultivable land due to globalization, less efficiency of nutrient, lack of nutrient availability and uptake is poor in soil, decreasing organic matter in soil, deficiency of water accessibility. In this critical situation it is more challenging to produce adequate food to feed the increasing populaces, which is projected to pass 9 billion by 2050. The nanofertilizer is ecologically safe and increase soil fertility, crop productivity and nutrient use efficacy. Nanofertilizer deals with atom-by-atom manipulation and the processes and products evolved are quite precise. Despite the fact that the nanotechnology is greatly exploited in the field of energy, environment and health, the research is agricultural sciences had just scratched the surface. Conversely, the importance and potentials of nanotechnology in agricultural sciences had been reviewed [1]. The nanofertilizers technology is very inventive and known to show economic benefit if the products evolved are economically viable and socially maintainable. These customized nanofertilizers are reported to decrease nutrient loss due to leaching, emissions in soil ecosystem [2].

Nano based encapsulated and slow release fertilizers increase the uptake of nutrients, enhance fertility of soil and decreasing toxic effects associated with over application of fertilizer. In Tamil Nadu Agricultural University, Coimbatore, various nano-zeolite based fertilizer research carried out with Nitrogen [3, 4], phosphorous [5], potassium [6], sulfur [7, 8] have been synthesized, characterized and examined in various crops.

Considering the above referred research, there is a crucial requirement to increase smart nanofertilizer can steadily release chemical substances to exact focused places and effectively control nutrient insufficiency. Nano based smart delivery system of nutrient to crop regulated slow release, target oriented and need based [9]. The important crop based nanofertilizer or nano formulation were produced which effectively increase growth and yield of the crops without create any harmful effect in environment ecosystem [10]. Nano fertilizer are less in size, more surface area, high sorption and desorption ability, slow release of nutrient for prolonged time. Conversely, the nanotechnology is new emerging science while using nanofertilizer to crop we have to conform safety measures to environment.

### **2. Technology of nano fertilizers**

The nano-fertilizer denotes in nano scale range to deliver nutrients to plant and also present invention which substitutes conventional fertilizer the nanofertilizer release and uptake of nutrients in the soil and crop is high [10]. The nano fertilizer will improve absorption of nutrient, potentially enhance photosynthesis, enhances the crop production [11]. The encapsulation technique is used to hold nutrient inside the carrier with polymer and steadily release nutrient to crop. The zeolite based nano porous fertilizer utilization and interest will increasing within young researchers in nano technology field [12, 13] nanofertilizer can enable nutrient carriage to the rhizosphere region and minimize nutrient loss and further improve use efficiency of applied fertilizer.

The nano fertilizers work carried out by [14] reported that using silica nano mesoporous particle to encapsulate urea and produce nano nitrogen slow release fertilizer [15] found that apatite as a source of nano phosphatic fertilizer will reduce the hazard and eutrophication problem in water ecosystem. The nano size in nature of fertilizer will enter into the plant cell is very easy without creating any ill effect [16] research reported that chitosan biodegradable polymeric molecule has been used as a source to produce nitrogen, phosphorous and potassium based nanofertilizer.

### **2.1 Important benefits of nanofertilizers**

Nanofertilizer innovative needed products for fertilizer industry and it's having higher surface area and auspicious picking for improving the quality and quantity of plants and seeds grown for consumption, to minimize production cost as well as ecofriendly to sustainable food production. The nanofertilizer are smaller in size, shape, charge of particle this will synthesized based on crop specific and demand oriented. Abundant particle like silver, titanium, zeolite, copper, silica, aluminum, carbon, zinc, and nitrogen based nanofertilizer is available.

Generally nanofertilizers are slow release: over a period of time the nutrient will available to crop at entire life cycle. Quick release: the outer most shell of the nano particle it breaks easily and quick release of nutrient in to the soil. Specific release: some specific chemicals molecules involve to break shell of the nano particle. Moisture release: in the presence of water molecules in nanofertilizer release nutrient in easy manner. Heat release: at a particular temperature nano particle get released. pH release: specific alkaline or acidic condition favor the slow release of nanofertilizer. The nano composite and fertilizers efficiently reduce nutrient loss from environment and increase use efficiency of nutrient [17, 18] found that nanofertilizer play important in agriculture production up to 35–40% to effectively reduce chronic problem, eutrophication, and nano fertilizer are alternative for conventional fertilizer.

**121**

*Novel Slow Release Nanocomposite Fertilizers DOI: http://dx.doi.org/10.5772/intechopen.93267*

• **Surface area:** The nanofertilizers possess small particle size which causes

increased surface area. Increased surface area raises the nanofertilizer reactivity with other compounds thereby increases the nutrient use efficiency and nutrient

• **Solubility:** Nano fertilizer with solvents as water possess increased solubility. Excessive solubility of nanofertilizers increases nutrient bioavailability in soil

decreased particle size the nanofertilizers diffuses into the plants and increases

• **Particles size:** Nanofertilizer has particle size of much <100 nm. Due to

• **Encapsulation of nanofertilizer:** Encapsulated nanofertilizer increases the available and nutrient uptake by plants [19]. Zeolite-based encapsulated nanofertilizers enhance availability of zinc and nitrogen to prevent from denitrification, volatilization, and leaching of nutrient in the soil.

• **Controlled release of fertilizers:** Controlled release of fertilizer decreases the toxicity of fertilizer. In peanut seeds Zinc oxide nano fertilizer produce increased growth of root and percentage of germination than bulk zinc

• **Nutrient uptake efficiency:** Nanofertilizers as increased uptake efficiency and

Zeolite mesoporous particle is potentially used for synthesis of nanofertilizer and its having higher surface area (900 m−2 g−1) of zeolite, making zeolite an extraordinarily effective ion exchange [22]. The surface area, excessive nutrient absorption ability, water holding capacity and internal micro pore numbers is high in nano sized zeolite mineral due to having desirable physical and chemical properties. Zeolite acts as a carrier of nitrogen, phosphorous, potassium and micronutrient

fertilizers prepared based on zeolite are successful of deliver nutrients up to 50 days in case of traditional fertilizer like urea ended with 10–12 days [25, 26] pronounced that ammonium and potassium encapsulated with clinoptilolite it will increase the solubility of nutrient to the crop reported that nano clay like zeolite and montmorillonite carrying nitrogen are ability to deliver prolonged period of time (>1000 h)

The increase nitrogen use efficiency by utilizing adsorbent of nano zeolites. The nitrogen use efficiency of conventional urea rarely exceeds 30–35% and nano zeolites has massive viable to normalize the discharge of nitrogen and nano zeolite encapsulated urea supports adsorption of nitrogen in higher zeolite mesoporous structure. The nitrogen content of zeourea and nano-zeourea confined 18.5 and 28% respectively release nitrogen 34–48 days in case of urea the nitrogen release arrest within 4 days [27, 28] proven that mixing urea with zeolite and sago waste water has extremely good advantage over urea alone as the combination increase the ammonium and available nitrate ions. The zeoponic is a plant grown with zeolite as a substrate

fertilizers enhance the productiveness of crops [23, 24]. Accordingly, nano-

by solubilization and spreading of insoluble nutrient in soil.

sulphate due to its controlled release nature [20].

limited leaching loss of applied fertilizers [21].

**2.3 Nanofertilizer prepared based on zeolite**

than conventional fertilizers (<500 h).

**2.2 Possessions of nanofertilizer**

the uptake of nutrients

uptake.

### **2.2 Possessions of nanofertilizer**

*Nanotechnology and the Environment*

**2. Technology of nano fertilizers**

use efficiency of applied fertilizer.

**2.1 Important benefits of nanofertilizers**

carbon, zinc, and nitrogen based nanofertilizer is available.

Considering the above referred research, there is a crucial requirement to increase smart nanofertilizer can steadily release chemical substances to exact focused places and effectively control nutrient insufficiency. Nano based smart delivery system of nutrient to crop regulated slow release, target oriented and need based [9]. The important crop based nanofertilizer or nano formulation were produced which effectively increase growth and yield of the crops without create any harmful effect in environment ecosystem [10]. Nano fertilizer are less in size, more surface area, high sorption and desorption ability, slow release of nutrient for prolonged time. Conversely, the nanotechnology is new emerging science while using nanofertilizer to crop we have to conform safety measures to environment.

The nano-fertilizer denotes in nano scale range to deliver nutrients to plant and also present invention which substitutes conventional fertilizer the nanofertilizer release and uptake of nutrients in the soil and crop is high [10]. The nano fertilizer will improve absorption of nutrient, potentially enhance photosynthesis, enhances the crop production [11]. The encapsulation technique is used to hold nutrient inside the carrier with polymer and steadily release nutrient to crop. The zeolite based nano porous fertilizer utilization and interest will increasing within young researchers in nano technology field [12, 13] nanofertilizer can enable nutrient carriage to the rhizosphere region and minimize nutrient loss and further improve

The nano fertilizers work carried out by [14] reported that using silica nano mesoporous particle to encapsulate urea and produce nano nitrogen slow release fertilizer [15] found that apatite as a source of nano phosphatic fertilizer will reduce the hazard and eutrophication problem in water ecosystem. The nano size in nature of fertilizer will enter into the plant cell is very easy without creating any ill effect [16] research reported that chitosan biodegradable polymeric molecule has been used as a source to produce nitrogen, phosphorous and potassium based nanofertilizer.

Nanofertilizer innovative needed products for fertilizer industry and it's having higher surface area and auspicious picking for improving the quality and quantity of plants and seeds grown for consumption, to minimize production cost as well as ecofriendly to sustainable food production. The nanofertilizer are smaller in size, shape, charge of particle this will synthesized based on crop specific and demand oriented. Abundant particle like silver, titanium, zeolite, copper, silica, aluminum,

Generally nanofertilizers are slow release: over a period of time the nutrient will available to crop at entire life cycle. Quick release: the outer most shell of the nano particle it breaks easily and quick release of nutrient in to the soil. Specific release: some specific chemicals molecules involve to break shell of the nano particle. Moisture release: in the presence of water molecules in nanofertilizer release nutrient in easy manner. Heat release: at a particular temperature nano particle get released. pH release: specific alkaline or acidic condition favor the slow release of nanofertilizer. The nano composite and fertilizers efficiently reduce nutrient loss from environment and increase use efficiency of nutrient [17, 18] found that nanofertilizer play important in agriculture production up to 35–40% to effectively reduce chronic problem, eutrophication, and nano fertilizer are alternative for conventional fertilizer.

**120**


### **2.3 Nanofertilizer prepared based on zeolite**

Zeolite mesoporous particle is potentially used for synthesis of nanofertilizer and its having higher surface area (900 m−2 g−1) of zeolite, making zeolite an extraordinarily effective ion exchange [22]. The surface area, excessive nutrient absorption ability, water holding capacity and internal micro pore numbers is high in nano sized zeolite mineral due to having desirable physical and chemical properties. Zeolite acts as a carrier of nitrogen, phosphorous, potassium and micronutrient fertilizers enhance the productiveness of crops [23, 24]. Accordingly, nanofertilizers prepared based on zeolite are successful of deliver nutrients up to 50 days in case of traditional fertilizer like urea ended with 10–12 days [25, 26] pronounced that ammonium and potassium encapsulated with clinoptilolite it will increase the solubility of nutrient to the crop reported that nano clay like zeolite and montmorillonite carrying nitrogen are ability to deliver prolonged period of time (>1000 h) than conventional fertilizers (<500 h).

The increase nitrogen use efficiency by utilizing adsorbent of nano zeolites. The nitrogen use efficiency of conventional urea rarely exceeds 30–35% and nano zeolites has massive viable to normalize the discharge of nitrogen and nano zeolite encapsulated urea supports adsorption of nitrogen in higher zeolite mesoporous structure. The nitrogen content of zeourea and nano-zeourea confined 18.5 and 28% respectively release nitrogen 34–48 days in case of urea the nitrogen release arrest within 4 days [27, 28] proven that mixing urea with zeolite and sago waste water has extremely good advantage over urea alone as the combination increase the ammonium and available nitrate ions. The zeoponic is a plant grown with zeolite as a substrate

and release demand driven nutrient delivery system [29]. The release of phosphorous from unmodified fertilizer loaded with zeolite and surface modified zeolite from strong potassium dihydrogen phosphate was once performed the use of the constant flow percolation reactor. The phosphorous supply from surface modified zeolite used to be available even after 1080 h of continuous percolation, while phosphorous from potassium dihydrogen phosphate was once exhausted within 264 h [30].

The nanoparticles, nano-zeolite as higher surface area due to this property it release fertilizers and anionic sulphate in slow and constant manner [31]. The pure ammonium sulphate and surface modified sulfur nano-zeolite were exposed to test nutrient release pattern by utilizing percolation reactors. The research data obviously designate that all of the available sulphate in pure ammonium sulphate is exhausted after 384 h while the launch of SO4 2− from sulphate loaded surface modified nano-zeolite is sustained even after 912 h, with concentrations ranging from 47.56 to 8.27 μg g−1. The surface modified nano sulfur is confirmed effective sulphure nanofertilizer as compared to conventional sulfur [32].

### **3. Formulation and preparation of nanofertilizer**

### **3.1 Nitrogen**

The urea treated with hydroxyapatite nanoparticles is attained by controlled adding of phosphoric acid into a suspension of Ca (OH)2 and urea, monitored by fast drying using spray dryer. The research found that release of urea from the nanohybrids with a 1:6 hydroxyapatite to urea ratio released urea 12 times more gradually associated to pure urea. Additionally, the nanohybrid confined very nearly the same quantity of available nitrogen as pure urea [33].

### **3.2 Phosphorus**

The encapsulated unmodified zeolite potassium dihydrogen phosphate release phosphorus from fertilizer and the percolation reactor used to test release pattern of surface modified zeolite from soil. The research found that the phosphorus source from fertilizer-loaded surface modified zeolite was accessible 1080 h of constant percolation, however phosphorus from potassium dihydrogen phosphate was arrest 264 h. This study confirmed that surface modified zeolite act as a potential nano fertilizer for phosphorus.

### **3.3 Potash**

Li and Zhang [20] described that potassium encapsulated with zeolite as a controlled release fertilizer and observed the hot pepper growth parameter and potassium dynamics in soil. The high cation exchange capacity of the nano clays is produced when silica (Si4+) is replaced by aluminum (Al3+) increase negative charge in the clay lattice. This negative charge is composed by cations such as ammonium, sodium, calcium, and potassium, which are interchangeable with other cations. Potash fertilizer is directly involved in photosynthesis process, it assist stomata opening in leaves and water storage. Potash fertilizer are released slowly by using Polyacrylamide-based coated pellets.

The fertilizer contribute 35–40% of crop productivity along with seed and proper irrigation. The imbalance use of fertilization especially urea it may create surface water nitrate pollution and deficiency of nitrogen in soil. In the earlier few decades, use efficiencies of nitrogen, phosphorous and potassium fertilizers

**123**

*Novel Slow Release Nanocomposite Fertilizers DOI: http://dx.doi.org/10.5772/intechopen.93267*

**4. Nutrient use efficiency and nanofertilizer**

quantities uptake in crop production.

have continued stable as 30–35%, 18–20%, 35–40% respectively. To overcome multi-nutrient deficiencies, imbalanced fertilization, low fertilizer use efficiency and decreasing soil organic matter it is crucial to develop a nano-based fertilizer for smart delivery of nutrient to targeted site. The application of nanofertilizer in foliar spray of 640 mg/ha foliar application (40 ppm concentration) of nano phosphorous gave 18 kg/ha phosphorous equal yield of cluster bean and pearl millet in arid environment condition. The research data propose that stable fertilization can also be deliver through nanotechnological approach to meet out crop demand and fertilizers encapsulated in nanoparticles will enhance the uptake of nutrients [34].

Enhancing nutrient use efficiency is a commendable goal and ultimate trial handled by agriculture fertilizer industry in worldwide. Presently nanofertilizer have involved with the experimental fields to increasing use efficiency of applied fertilizer. The nanofertilizer consist of higher surface area because lesser in size of the nanoparticle and have high reactivity, solubility in water. The nano encapsulation techniques considered as three ways: (a) nutrient can be encapsulation inside nanoporous particle, (b) A thin polymer can be used for outer coating (c) Can be released nanosize level fertilizer. Zeolite based nano encapsulated fertilizer is ability to release

nutrient in slowly in to the crops and increase nutrient use efficiency [35].

In the conventional fertilizer the 50–70% of low in nitrogen use efficiency. New smart delivery systems of nano technological approach is enhance nitrogen availability and use efficiency. The fertilizer use effectivity in 10–25% for phosphorus. With nano-fertilizers rising as substitutes to traditional fertilizers, buildup of nutrient in soils and thereby eutrophication and drinking water impurity may additionally be eliminated. In fact, nanotechnology has opened up new opportunities to enhance nutrient use efficiency and limit charges of environmental protection. The encapsulation techniques such as manganese core shell will help to uptake and slow release of nutrient need based (5). Maximum number of agricultural soils in India have low native fertility and effective and continuous crop production on these soils needs regular nutrient efforts. The considerable available of nutrients for recycling through animal manures and crop residues is significantly insufficient to reimburse for the

However, the use of conventional fertilizers in worldwide improved progressively over a period of time the use efficiency of nutrients applied as fertilizers continues to remain terribly low in phosphorous (15–20%) and micronutrients (2–5%) like zinc, iron, copper. When nutrient inputs are used incompetently then both cost of farming and threat of biosphere pollution rise. Thus, the economy and ecology highlights the obsessive need for more effective use of nutrients in crop production. Since, fertilizer nutrients are exclusive and used in huge quantities at national level, any rise in use efficiency will lead to a considerable cut in nutrient necessity and huge economic advantage at national level [36]. The slow-release properties of Zn to plants may be closely associated with higher yields. Nanotechnology has great potential in agriculture as it can enhance the quality of life through its application in fields like sustainable and

quality agriculture, and improved and rich food for the community [37, 38].

The utility of nanostructures or nanoparticles as agrochemicals (fertilizers or pesticides) is systematically being explored, before nanofertilizers may want to

**5. Environmental and health situation of nanofertilizers**

*Novel Slow Release Nanocomposite Fertilizers DOI: http://dx.doi.org/10.5772/intechopen.93267*

*Nanotechnology and the Environment*

**3.1 Nitrogen**

**3.2 Phosphorus**

**3.3 Potash**

fertilizer for phosphorus.

Polyacrylamide-based coated pellets.

and release demand driven nutrient delivery system [29]. The release of phosphorous from unmodified fertilizer loaded with zeolite and surface modified zeolite from strong potassium dihydrogen phosphate was once performed the use of the constant flow percolation reactor. The phosphorous supply from surface modified zeolite used to be available even after 1080 h of continuous percolation, while phosphorous from

The nanoparticles, nano-zeolite as higher surface area due to this property it release fertilizers and anionic sulphate in slow and constant manner [31]. The pure ammonium sulphate and surface modified sulfur nano-zeolite were exposed to test nutrient release pattern by utilizing percolation reactors. The research data obviously designate that all of the available sulphate in pure ammonium sulphate

modified nano-zeolite is sustained even after 912 h, with concentrations ranging from 47.56 to 8.27 μg g−1. The surface modified nano sulfur is confirmed effective

The urea treated with hydroxyapatite nanoparticles is attained by controlled adding of phosphoric acid into a suspension of Ca (OH)2 and urea, monitored by fast drying using spray dryer. The research found that release of urea from the nanohybrids with a 1:6 hydroxyapatite to urea ratio released urea 12 times more gradually associated to pure urea. Additionally, the nanohybrid confined very

The encapsulated unmodified zeolite potassium dihydrogen phosphate release phosphorus from fertilizer and the percolation reactor used to test release pattern of surface modified zeolite from soil. The research found that the phosphorus source from fertilizer-loaded surface modified zeolite was accessible 1080 h of constant percolation, however phosphorus from potassium dihydrogen phosphate was arrest 264 h. This study confirmed that surface modified zeolite act as a potential nano

Li and Zhang [20] described that potassium encapsulated with zeolite as a controlled release fertilizer and observed the hot pepper growth parameter and potassium dynamics in soil. The high cation exchange capacity of the nano clays is produced when silica (Si4+) is replaced by aluminum (Al3+) increase negative charge in the clay lattice. This negative charge is composed by cations such as ammonium, sodium, calcium, and potassium, which are interchangeable with other cations. Potash fertilizer is directly involved in photosynthesis process, it assist stomata opening in leaves and water storage. Potash fertilizer are released slowly by using

The fertilizer contribute 35–40% of crop productivity along with seed and proper irrigation. The imbalance use of fertilization especially urea it may create surface water nitrate pollution and deficiency of nitrogen in soil. In the earlier few decades, use efficiencies of nitrogen, phosphorous and potassium fertilizers

2− from sulphate loaded surface

potassium dihydrogen phosphate was once exhausted within 264 h [30].

sulphure nanofertilizer as compared to conventional sulfur [32].

nearly the same quantity of available nitrogen as pure urea [33].

**3. Formulation and preparation of nanofertilizer**

is exhausted after 384 h while the launch of SO4

**122**

have continued stable as 30–35%, 18–20%, 35–40% respectively. To overcome multi-nutrient deficiencies, imbalanced fertilization, low fertilizer use efficiency and decreasing soil organic matter it is crucial to develop a nano-based fertilizer for smart delivery of nutrient to targeted site. The application of nanofertilizer in foliar spray of 640 mg/ha foliar application (40 ppm concentration) of nano phosphorous gave 18 kg/ha phosphorous equal yield of cluster bean and pearl millet in arid environment condition. The research data propose that stable fertilization can also be deliver through nanotechnological approach to meet out crop demand and fertilizers encapsulated in nanoparticles will enhance the uptake of nutrients [34].

### **4. Nutrient use efficiency and nanofertilizer**

Enhancing nutrient use efficiency is a commendable goal and ultimate trial handled by agriculture fertilizer industry in worldwide. Presently nanofertilizer have involved with the experimental fields to increasing use efficiency of applied fertilizer. The nanofertilizer consist of higher surface area because lesser in size of the nanoparticle and have high reactivity, solubility in water. The nano encapsulation techniques considered as three ways: (a) nutrient can be encapsulation inside nanoporous particle, (b) A thin polymer can be used for outer coating (c) Can be released nanosize level fertilizer. Zeolite based nano encapsulated fertilizer is ability to release nutrient in slowly in to the crops and increase nutrient use efficiency [35].

In the conventional fertilizer the 50–70% of low in nitrogen use efficiency. New smart delivery systems of nano technological approach is enhance nitrogen availability and use efficiency. The fertilizer use effectivity in 10–25% for phosphorus. With nano-fertilizers rising as substitutes to traditional fertilizers, buildup of nutrient in soils and thereby eutrophication and drinking water impurity may additionally be eliminated. In fact, nanotechnology has opened up new opportunities to enhance nutrient use efficiency and limit charges of environmental protection. The encapsulation techniques such as manganese core shell will help to uptake and slow release of nutrient need based (5). Maximum number of agricultural soils in India have low native fertility and effective and continuous crop production on these soils needs regular nutrient efforts. The considerable available of nutrients for recycling through animal manures and crop residues is significantly insufficient to reimburse for the quantities uptake in crop production.

However, the use of conventional fertilizers in worldwide improved progressively over a period of time the use efficiency of nutrients applied as fertilizers continues to remain terribly low in phosphorous (15–20%) and micronutrients (2–5%) like zinc, iron, copper. When nutrient inputs are used incompetently then both cost of farming and threat of biosphere pollution rise. Thus, the economy and ecology highlights the obsessive need for more effective use of nutrients in crop production. Since, fertilizer nutrients are exclusive and used in huge quantities at national level, any rise in use efficiency will lead to a considerable cut in nutrient necessity and huge economic advantage at national level [36]. The slow-release properties of Zn to plants may be closely associated with higher yields. Nanotechnology has great potential in agriculture as it can enhance the quality of life through its application in fields like sustainable and quality agriculture, and improved and rich food for the community [37, 38].

### **5. Environmental and health situation of nanofertilizers**

The utility of nanostructures or nanoparticles as agrochemicals (fertilizers or pesticides) is systematically being explored, before nanofertilizers may want to

be used in agriculture or farming for a general farm practice. The homes of many nanoparticles are viewed to be of attainable hazard to human health, viz., size, shape, solubility, crystal phase, type of material, and exposure and dosage concentrations. However, specialist opinions indicate that food products containing nanoparticles available in the market are probably protected to eat, but this is an area that needs to be more actively investigated. To address the protection challenge element research are required to know the effect of nanoparticles within the human body once exposed through nanofood. Researchers have to assess and improve suited evaluation techniques to investigate the impact of nanoparticles and nanofertilizers on biotic and abiotic factors of ecosystem. Among the various issues, the accumulation of nanomaterials in environment, edible part of plants would possibly be the necessary issues earlier than use in agriculture.

### **6. Conclusion**

World population is increasing geometrically its great agricultural challenge for feed the developing population with nutritious food. The biotic and abiotic constraints which limits the agricultural productivity furthermore has an effect on human health and use of exclusive nanofertilizers to improving crop production in agriculture. Consequently, it is required to attentively study the association of nanoparticle and crop microbiome. Supplementary, in order to recognize the interface of nanoparticle with soil and environment ecosystem. Investigational confirmation of the allowable use of nanofertilizer quantity within safety limits need to be described. The interface of nanomaterials with soil and plants varies with the type of nanofertilizer the applied attention of nanoparticle the time of treatment, plant genotype and the stage of growth. Regardless of these possible benefits, the recommendation of nanofertilizer in crop enhancement could come with hazards for the environment non-target plants, useful soil organism affected if nano-materials are misrepresented.

### **Author details**

Muthuraman Yuvaraj1 \* and Kizhaeral Sevathapandian Subramanian<sup>2</sup>


\*Address all correspondence to: yuvasoil@gmail.com

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

**125**

2004;**15**:138-140

*Novel Slow Release Nanocomposite Fertilizers DOI: http://dx.doi.org/10.5772/intechopen.93267*

> International Conference on Nanoagri. Brazil: Sao Pedro; 2010. pp. 28-33

[10] DeRosa MC, Monreal C, Schnitzer M, Walsh R, Sultan Y. Nanotechnology in fertilizers. Nature Nanotechnology.

2010;**32**(5):1234-1237

[11] Fageria NK. Influence of micronutrients on dry matter yield and interaction with other nutrients in annual crops. Pesquisa Agropecuária

Brasileira. 2002;**37**:1765-1772

Science and Technology. 2013;**47**:10645-10652

2010;**44**(7):2360-2370

2016;**304**:291-305

2013;**41**:201-207

[15] Jaberzadeh A, Moaveni P,

[16] Jayvanth Kumar U, Vijay Bahadur S, Prasad VM, Shukla PK. Effect of different concentrations of Iron oxide and zinc oxide nanoparticles on growth and yield of strawberry (*Fragaria x ananassa* Duch) cv. Chandler. International Journal of

Moghadam HRT, Zahedi H. Influence of bulk and nanoparticles titanium foliar application on some agronomic traits, seed gluten and starch contents of wheat subjected to water deficit stress. Notulae Botanicae Horti Agrobotanici Cluj.

[12] Ghafariyan M, Malakouti H, Dadpour MJ, Stroeve MR, Mahmoudi P. Effects of magnetite nanoparticles on soybean chlorophyll. Environmental

[13] He F, Zhao DY, Paul C. Field assessment of carboxymethyl cellulose stabilized iron nanoparticles for in situ destruction of chlorinated solvents in source zones. Water Research.

[14] Hossain Z, Mustafa G, Sakata K, Komatsu S. Insights into the proteomic response of soybean towards Al2O3, ZnO, and Ag nanoparticles stress. Journal of Hazardous Materials.

[1] Ahmed OH, Hussin A, Mohd Hanif Ahmad H, Boyie Jalloh M, Abd Rahim A, Muhamad Majid N. Ammonia volatilization and ammonium accumulation from urea mixed with zeolite and triple superphosphate. Acta Agriculturae Scandinavica, Section B.

[2] Anderson K. Economic impacts of policies affecting crop biotechnology and trade. New Biotechnology. 2010;**27**:558-564. DOI: 10.1016/j.

[3] Andow D, Hutchison W. Bt-Corn Resistance Management. Now or Never: Serious New Plans to Save Natural Pest Control. Cambridge, MA: Union of Concerned Scientists; 1998. pp. 18-64

[4] Andrews RD, Shaw JW. 2010. Available from: http://www.zeoponix.

[6] Apel A. The costly benefits of opposing agricultural biotechnology. New Biotechnology. 2010;**27**:635-675

[8] Bao-shan L, Shao-qi D, Chun-hui L, Li-jun F, Shu-chun Q, Min Y. Effect of TMS (nanostructured silicon dioxide) on growth of Changbai larch seedlings. Journal of Forest Research.

[9] Cui HX, Sun CJ, Liu Q, Jiang J, Gu W. Applications of nanotechnology in agrochemical formulation, perspectives,

challenges and strategies. In:

[7] Bansiwal AK, Rayalu SS, Labhasetwar NK, Juwarkar AA, Devotta S. Surfactant-modified zeolite as a slow release fertilizer for phosphorus. Journal of Agricultural and Food Chemistry. 2006;**54**:4773-4779

[5] Antoniou M. Genetically engineered food—Panacea or Pandora's box. Nutrition Today. 1996;**6**:8-11

com/new-page-5.htm

**References**

2001;**58**(2):182-186

nbt.2010.05.012

*Novel Slow Release Nanocomposite Fertilizers DOI: http://dx.doi.org/10.5772/intechopen.93267*

### **References**

*Nanotechnology and the Environment*

be the necessary issues earlier than use in agriculture.

**124**

**Author details**

**6. Conclusion**

Muthuraman Yuvaraj1

nano-materials are misrepresented.

\* and Kizhaeral Sevathapandian Subramanian<sup>2</sup>

1 Agricultural College and Research Institute, Tiruvannamalai, Tamil Nadu, India

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

be used in agriculture or farming for a general farm practice. The homes of many nanoparticles are viewed to be of attainable hazard to human health, viz., size, shape, solubility, crystal phase, type of material, and exposure and dosage concentrations. However, specialist opinions indicate that food products containing nanoparticles available in the market are probably protected to eat, but this is an area that needs to be more actively investigated. To address the protection challenge element research are required to know the effect of nanoparticles within the human body once exposed through nanofood. Researchers have to assess and improve suited evaluation techniques to investigate the impact of nanoparticles and nanofertilizers on biotic and abiotic factors of ecosystem. Among the various issues, the accumulation of nanomaterials in environment, edible part of plants would possibly

World population is increasing geometrically its great agricultural challenge for feed the developing population with nutritious food. The biotic and abiotic constraints which limits the agricultural productivity furthermore has an effect on human health and use of exclusive nanofertilizers to improving crop production in agriculture. Consequently, it is required to attentively study the association of nanoparticle and crop microbiome. Supplementary, in order to recognize the interface of nanoparticle with soil and environment ecosystem. Investigational confirmation of the allowable use of nanofertilizer quantity within safety limits need to be described. The interface of nanomaterials with soil and plants varies with the type of nanofertilizer the applied attention of nanoparticle the time of treatment, plant genotype and the stage of growth. Regardless of these possible benefits, the recommendation of nanofertilizer in crop enhancement could come with hazards for the environment non-target plants, useful soil organism affected if

2 Tamil Nadu Agricultural University, Coimbatore, India

\*Address all correspondence to: yuvasoil@gmail.com

provided the original work is properly cited.

[1] Ahmed OH, Hussin A, Mohd Hanif Ahmad H, Boyie Jalloh M, Abd Rahim A, Muhamad Majid N. Ammonia volatilization and ammonium accumulation from urea mixed with zeolite and triple superphosphate. Acta Agriculturae Scandinavica, Section B. 2001;**58**(2):182-186

[2] Anderson K. Economic impacts of policies affecting crop biotechnology and trade. New Biotechnology. 2010;**27**:558-564. DOI: 10.1016/j. nbt.2010.05.012

[3] Andow D, Hutchison W. Bt-Corn Resistance Management. Now or Never: Serious New Plans to Save Natural Pest Control. Cambridge, MA: Union of Concerned Scientists; 1998. pp. 18-64

[4] Andrews RD, Shaw JW. 2010. Available from: http://www.zeoponix. com/new-page-5.htm

[5] Antoniou M. Genetically engineered food—Panacea or Pandora's box. Nutrition Today. 1996;**6**:8-11

[6] Apel A. The costly benefits of opposing agricultural biotechnology. New Biotechnology. 2010;**27**:635-675

[7] Bansiwal AK, Rayalu SS, Labhasetwar NK, Juwarkar AA, Devotta S. Surfactant-modified zeolite as a slow release fertilizer for phosphorus. Journal of Agricultural and Food Chemistry. 2006;**54**:4773-4779

[8] Bao-shan L, Shao-qi D, Chun-hui L, Li-jun F, Shu-chun Q, Min Y. Effect of TMS (nanostructured silicon dioxide) on growth of Changbai larch seedlings. Journal of Forest Research. 2004;**15**:138-140

[9] Cui HX, Sun CJ, Liu Q, Jiang J, Gu W. Applications of nanotechnology in agrochemical formulation, perspectives, challenges and strategies. In:

International Conference on Nanoagri. Brazil: Sao Pedro; 2010. pp. 28-33

[10] DeRosa MC, Monreal C, Schnitzer M, Walsh R, Sultan Y. Nanotechnology in fertilizers. Nature Nanotechnology. 2010;**32**(5):1234-1237

[11] Fageria NK. Influence of micronutrients on dry matter yield and interaction with other nutrients in annual crops. Pesquisa Agropecuária Brasileira. 2002;**37**:1765-1772

[12] Ghafariyan M, Malakouti H, Dadpour MJ, Stroeve MR, Mahmoudi P. Effects of magnetite nanoparticles on soybean chlorophyll. Environmental Science and Technology. 2013;**47**:10645-10652

[13] He F, Zhao DY, Paul C. Field assessment of carboxymethyl cellulose stabilized iron nanoparticles for in situ destruction of chlorinated solvents in source zones. Water Research. 2010;**44**(7):2360-2370

[14] Hossain Z, Mustafa G, Sakata K, Komatsu S. Insights into the proteomic response of soybean towards Al2O3, ZnO, and Ag nanoparticles stress. Journal of Hazardous Materials. 2016;**304**:291-305

[15] Jaberzadeh A, Moaveni P, Moghadam HRT, Zahedi H. Influence of bulk and nanoparticles titanium foliar application on some agronomic traits, seed gluten and starch contents of wheat subjected to water deficit stress. Notulae Botanicae Horti Agrobotanici Cluj. 2013;**41**:201-207

[16] Jayvanth Kumar U, Vijay Bahadur S, Prasad VM, Shukla PK. Effect of different concentrations of Iron oxide and zinc oxide nanoparticles on growth and yield of strawberry (*Fragaria x ananassa* Duch) cv. Chandler. International Journal of

Current Microbiology and Applied Sciences. 2017;**6**(8):2440-2445

[17] Johnston ML. Soil Chemical Analysis. New Delhi: Prentice Hall of India Private Ltd.; 2010. pp. 56-70

[18] Lal R. Soils and India's food security. Journal of the Indian Society of Soil Science. 2008;**56**(2):129-138

[19] Latifah O, Ahmed OH, Nik Muhamad AM. Reducing ammonia loss from urea and improving soil exchangeable ammonium and available nitrate in non-waterlogged soils through mixing zeolite and sago (*Metroxylon sagu*) waste water. International Journal of Physical Sciences. 2011;**6**(4):866-870

[20] Li Z, Zhang Y. Use of surfactant modified zeolite to carry and slowly release sulfate. Desalination and Water Treatment. 2010;**21**:73-78

[21] Lin D, Xing B. Root uptake and phytotoxicity of ZnO nanoparticles. Environmental Science & Technology. 2008;**42**:5580-5585

[22] Liu R, Lal R. Synthetic apatite nanoparticles as a phosphorus fertilizer for soybean (*Glycine max*). Scientific Reports. 2014;**4**:5686

[23] Mahajan P, Shailesh K, Dhoke RK, Anand K. Effect of nanoparticles suspension on the growth of mung (Vigna radiata) seedlings by foliar spray method. Nanotechnology. 2013;**3**:4052-4081

[24] Mahmoodzadeh H, Nabavi M, Kashefi H. Effect of nanoscale titanium dioxide particles on the germination and growth of canola (*Brassica napus*). Journal of Ornamental and Horticultural Plants. 2013;**3**:25-32

[25] Malhi SS, Haderlin LK, Pauly DG, Johnson AM. Improving fertiliser use efficiency. Better Crops. 2002;**86**:22-25 [26] Manikandan A, Subramanian KS. Fabrication and characterisation of nanoporous zeolite based N fertilizer. African Journal of Agricultural Research. 2014;**9**(2):276-284

[27] Markovich A, Takac A, Illin Z, Ito T, Tognoni F. Enriched zeolites as substrate component in the production of paper and tomato seedling. Acta Horticulturae. 1995;**39**(6):321-328

[28] Meena DS. M.Sc. (Agri.) thesis, Dharwad, Karnataka (India): University of Agricultural Sciences; 2015

[29] Mishra V, Mishra RK, Dikshit A, Pandey AC. Interactions of nanoparticles with plants, an emerging prospective in the agriculture industry. In: Ahmad P, Rasool S, editors. Emerging Technologies and Management of Crop Stress Tolerance, Biological Techniques. Vol. 1. USA: Academic Press; 2014. pp. 159-180

[30] Mohanraj J. Effect of nano-zeolite on nitrogen dynamics and greenhouse gas emission in rice soil eco system [M.Tech. thesis]. Coimbatore: Tamil Nadu Agricultural University; 2013

[31] Mukhopadhyay D, Majumdar K, Patil R, Mandal MK. Response of rainfed rice to soil test-based nutrient application in Terai alluvial soils. Better Crops. 2008;**92**:13-15

[32] Naderi MR, Danesh Shahraki A. Nanofertilizers and their role in sustainable agriculture. International Journal of Agriculture and Crop Sciences. 2013;**5**:2229-2232

[33] Nair R, Varghese SH, Nair BG, Maekawa T, Yoshida Y, Kumar DS. Nanoparticulate material delivery to plants. Plant Science. 2010;**179**:154-163

[34] Pickering HW, Menzies NW, Hunter MN. Zeolite rock phosphate-a novel slow release phosphorus fertiliser

**127**

*Novel Slow Release Nanocomposite Fertilizers DOI: http://dx.doi.org/10.5772/intechopen.93267*

for potted plant production. Scientia Horticulturae. 2002;**9**(4):333-343

[35] Prasad TNV, Sudhakar KVP, Sreenivasulu Y, Latha P, Munaswamy V, Raja Reddy K, et al. Effect of nanoscale zinc oxide particles on the germination, growth and yield of peanut. Journal of Plant Nutrition. 2012;**356**:905-927

[36] Raliya R. Application of nanoparticles on plant system and associated rhizospheric rhizobacteria. Digest Journal of Nanomaterials and Biostructures. 2012;**4**:587-592

[37] Yuvaraj M, Subramanian KS. Controlled-release fertilizer of zinc encapsulated by a manganese hollow core shell. Soil Science and Plant Nutrition. 2015;**61**(2):319-326. DOI: 10.1080/00380768.2014.979327

[38] Yuvaraj M, Subramanian KS. Development of slow release Zn fertilizer using nano-zeolite as carrier. Journal of Plant Nutrition.

2018;**41**(3):311-320. DOI: 10.1080/01904167.2017.1381729 *Novel Slow Release Nanocomposite Fertilizers DOI: http://dx.doi.org/10.5772/intechopen.93267*

for potted plant production. Scientia Horticulturae. 2002;**9**(4):333-343

*Nanotechnology and the Environment*

Current Microbiology and Applied Sciences. 2017;**6**(8):2440-2445

[26] Manikandan A, Subramanian KS. Fabrication and characterisation of nanoporous zeolite based N fertilizer. African Journal of Agricultural Research. 2014;**9**(2):276-284

[27] Markovich A, Takac A, Illin Z, Ito T, Tognoni F. Enriched zeolites as substrate component in the production of paper and tomato seedling. Acta Horticulturae.

[28] Meena DS. M.Sc. (Agri.) thesis, Dharwad, Karnataka (India): University

Dikshit A, Pandey AC. Interactions of nanoparticles with plants, an

emerging prospective in the agriculture industry. In: Ahmad P, Rasool S, editors. Emerging Technologies and Management of Crop Stress Tolerance, Biological Techniques. Vol. 1. USA: Academic Press; 2014. pp. 159-180

[30] Mohanraj J. Effect of nano-zeolite on nitrogen dynamics and greenhouse gas emission in rice soil eco system [M.Tech. thesis]. Coimbatore: Tamil Nadu Agricultural University; 2013

[31] Mukhopadhyay D, Majumdar K, Patil R, Mandal MK. Response of rainfed

application in Terai alluvial soils. Better

[32] Naderi MR, Danesh Shahraki A. Nanofertilizers and their role in sustainable agriculture. International Journal of Agriculture and Crop Sciences. 2013;**5**:2229-2232

[33] Nair R, Varghese SH, Nair BG, Maekawa T, Yoshida Y, Kumar DS. Nanoparticulate material delivery to plants. Plant Science. 2010;**179**:154-163

[34] Pickering HW, Menzies NW, Hunter MN. Zeolite rock phosphate-a novel slow release phosphorus fertiliser

rice to soil test-based nutrient

Crops. 2008;**92**:13-15

of Agricultural Sciences; 2015

[29] Mishra V, Mishra RK,

1995;**39**(6):321-328

[17] Johnston ML. Soil Chemical Analysis. New Delhi: Prentice Hall of India Private Ltd.; 2010. pp. 56-70

Science. 2008;**56**(2):129-138

[19] Latifah O, Ahmed OH, Nik Muhamad AM. Reducing ammonia loss from urea and improving soil exchangeable ammonium and available nitrate in non-waterlogged soils through mixing zeolite and sago (*Metroxylon sagu*) waste water. International Journal of Physical Sciences. 2011;**6**(4):866-870

[20] Li Z, Zhang Y. Use of surfactant modified zeolite to carry and slowly release sulfate. Desalination and Water

[21] Lin D, Xing B. Root uptake and phytotoxicity of ZnO nanoparticles. Environmental Science & Technology.

[22] Liu R, Lal R. Synthetic apatite nanoparticles as a phosphorus fertilizer for soybean (*Glycine max*). Scientific

[23] Mahajan P, Shailesh K, Dhoke RK, Anand K. Effect of nanoparticles suspension on the growth of mung (Vigna radiata) seedlings by foliar spray method. Nanotechnology.

[24] Mahmoodzadeh H, Nabavi M, Kashefi H. Effect of nanoscale titanium dioxide particles on the germination and growth of canola (*Brassica napus*). Journal of Ornamental and Horticultural Plants. 2013;**3**:25-32

[25] Malhi SS, Haderlin LK, Pauly DG, Johnson AM. Improving fertiliser use efficiency. Better Crops. 2002;**86**:22-25

Treatment. 2010;**21**:73-78

2008;**42**:5580-5585

Reports. 2014;**4**:5686

2013;**3**:4052-4081

[18] Lal R. Soils and India's food security. Journal of the Indian Society of Soil

**126**

[35] Prasad TNV, Sudhakar KVP, Sreenivasulu Y, Latha P, Munaswamy V, Raja Reddy K, et al. Effect of nanoscale zinc oxide particles on the germination, growth and yield of peanut. Journal of Plant Nutrition. 2012;**356**:905-927

[36] Raliya R. Application of nanoparticles on plant system and associated rhizospheric rhizobacteria. Digest Journal of Nanomaterials and Biostructures. 2012;**4**:587-592

[37] Yuvaraj M, Subramanian KS. Controlled-release fertilizer of zinc encapsulated by a manganese hollow core shell. Soil Science and Plant Nutrition. 2015;**61**(2):319-326. DOI: 10.1080/00380768.2014.979327

[38] Yuvaraj M, Subramanian KS. Development of slow release Zn fertilizer using nano-zeolite as carrier. Journal of Plant Nutrition. 2018;**41**(3):311-320. DOI: 10.1080/01904167.2017.1381729

**129**

**Chapter 8**

**Abstract**

environment.

chemical reduction

**1. Introduction**

*Navin Kumar Mogha*

Graphene Oxide-Based

Nanohybrids as Pesticide

Biosensors: Latest Developments

Graphene is the most significant two-dimensional nanomaterial with sp2 hybridized carbon atoms in a honeycomb arrangement with an extremely high surface area, excellent electrical properties, high mechanical strength, and advantageous optical properties and is relatively easy to functionalize and mass produce. Various inorganic nanoparticles incorporated with graphene, such as gold, silver, and palladium nanoparticles are brought into sharp focus due to their catalytic, optical, electronic, and quantized charging/discharging properties. Graphene oxide-based nanohybrids are particularly well suited for biosensing applications and catalysis. Consequently, this area of research has grown to represent one of the largest classes within the scope of materials science and is rapidly becoming a key area in nanoscience and nanotechnology offering significant potential in the development of advanced materials in multiple and diverse applications. Here in this present chapter, synthesis, characterization of graphene oxide, and their nanohybrids are discussed thoroughly with their application in the field of pesticide biosensors. This chapter will help in a further understanding of graphene-based nanohybrids as a biosensing platform for their future applications in a sustainable

**Keywords:** graphene oxide, pesticides, biosensors, nanohybrids, nanoparticles,

The prevalence of harmful and toxic chemical compounds in the environment has become a serious issue in recent decades [1]. Contamination of foodstuffs, drinking water, and air with hazardous pollutants and other foreign substances are real and a direct threat to human health, whereas the accumulation of such contaminants in the human body and environment may lead to long-lasting, severe, and harmful effects after primary exposure [2]. Chemicals such as pesticides, plastic, lead, methylmercury, polychlorinated biphenyls, arsenic, toluene, rubber, and paper [3] play a key role in the economic growth of countries to fulfill their development objectives [4]. The term "pesticide" is defined as any chemical entity, which has the ability to kill the various kinds of pests including rodents, insects, fungi, weeds, etc. and henceforth categorized accordingly as rodenticides, insecticides, fungicides, and herbicides [5]. However, based on chemical composition, pesticides can be classified into five main groups as organochlorines, organophosphorus (OP), carbamates,

### **Chapter 8**

## Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments

*Navin Kumar Mogha*

### **Abstract**

Graphene is the most significant two-dimensional nanomaterial with sp2 hybridized carbon atoms in a honeycomb arrangement with an extremely high surface area, excellent electrical properties, high mechanical strength, and advantageous optical properties and is relatively easy to functionalize and mass produce. Various inorganic nanoparticles incorporated with graphene, such as gold, silver, and palladium nanoparticles are brought into sharp focus due to their catalytic, optical, electronic, and quantized charging/discharging properties. Graphene oxide-based nanohybrids are particularly well suited for biosensing applications and catalysis. Consequently, this area of research has grown to represent one of the largest classes within the scope of materials science and is rapidly becoming a key area in nanoscience and nanotechnology offering significant potential in the development of advanced materials in multiple and diverse applications. Here in this present chapter, synthesis, characterization of graphene oxide, and their nanohybrids are discussed thoroughly with their application in the field of pesticide biosensors. This chapter will help in a further understanding of graphene-based nanohybrids as a biosensing platform for their future applications in a sustainable environment.

**Keywords:** graphene oxide, pesticides, biosensors, nanohybrids, nanoparticles, chemical reduction

### **1. Introduction**

The prevalence of harmful and toxic chemical compounds in the environment has become a serious issue in recent decades [1]. Contamination of foodstuffs, drinking water, and air with hazardous pollutants and other foreign substances are real and a direct threat to human health, whereas the accumulation of such contaminants in the human body and environment may lead to long-lasting, severe, and harmful effects after primary exposure [2]. Chemicals such as pesticides, plastic, lead, methylmercury, polychlorinated biphenyls, arsenic, toluene, rubber, and paper [3] play a key role in the economic growth of countries to fulfill their development objectives [4]. The term "pesticide" is defined as any chemical entity, which has the ability to kill the various kinds of pests including rodents, insects, fungi, weeds, etc. and henceforth categorized accordingly as rodenticides, insecticides, fungicides, and herbicides [5]. However, based on chemical composition, pesticides can be classified into five main groups as organochlorines, organophosphorus (OP), carbamates, pyrethrin, and pyrethroids compound. The unnecessary consumption of those agrochemicals has undesirable effects on the ecosystem, including a decreased population of beneficial insects as well as risks to vulnerable species and bird habitats. Pesticide pollution is becoming one of the most severe challenges of common public health around the globe because of their particular application in the agriculture sector to assure crop yield and productivity [6]. In some cases, acute poisoning may occur because of inappropriate handling that ultimately causes adverse health effects because of long-term and low-level exposures. The widespread diffusion of such toxic chemicals adversely affects a great part of the population. A large number of people, categorized by different patterns, ages, and degrees of exposure, are at increased risk to the adverse effects of these chemicals. Workers who are involved in the manufacturing and application of pesticides are at a considerable risk of exposure, which typically occurs among specific users in public health. In the agricultural sector, farmers may get direct exposure to pesticides during spraying across the agricultural fields [7, 8]. In the general population, individuals may be at a risk of pesticide exposure on a daily basis in food and drinking water or to pesticide drift in domestic areas adjacent to spraying areas [9]. Given their hazardous effect on human health and the environment, the prime concern should be of their rapid and reliable detection by a convenient method. Although various laboratory-based analytical methods such as colorimetry, capillary electrophoresis (CE), thin-layer chromatography (TLC), gas-liquid chromatography(GLC), high-performance liquid chromatography (HPLC), nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and enzyme-linked immunosorbent assays (ELISA) have been employed so far, but these suffer from one and the other drawback such as the use of expensive instrumentation, time-consuming process, and requirement of trained personnel [5]. Therefore, there is a dire need to develop sensitive, rapid, economically feasible, and easy-to-use methods for the detection of these compounds in the environment. Such efficient detection methods could be developed using biosensors that are used in a variety of applications for prompt and accurate detection of different analytes such as biomolecules and chemical compounds [10]. Various nanomaterials are generally categorized into nanoparticles, nanotubes, and nanocomposites, which can be generally employed for the diagnosis, degradation, and adsorption of chemical pesticides. Carbon nanomaterials or nanoparticles (NPs) have specific characteristics, including a high surface-to-volume ratio, good electrical conductivity, catalytic action, and beneficial biocompatibility and can be simply modified with functional groups, which has made them be often used in pesticide biosensors to boost analytical efficiency [11].

It is well known that graphite and diamond are its most common allotropic form of carbon found in nature. Graphite, which is found as a natural mineral, consists of sp2 hybridized carbon atomic layers that are stacked collectively through weak attraction forces such as van der Waals forces. Single-layer out of these carbon atomic layers are packed in a two-dimensional honeycomb structure called as "graphene" termed coined by Boehm et al. [12]. It remains almost impossible to isolate graphene monolayer for several decades before Geim and Novoselov [13] who reported a scotch tape method or micromechanical cleavage method for the isolation of graphene monolayer from silicon oxide substrate. Discovery of graphene monolayer awarded Geim and Novoselov the Nobel Prize in Physics "for groundbreaking experiments regarding the two-dimensional material graphene".

Graphene, which consists of a one-atom-thick planar sheet comprising an sp2 -bonded carbon structure with exceptionally high crystal and electronic quality, is a novel material that has emerged as a rapidly rising star in the field of material science [14, 15].

**131**

**Figure 1.**

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments*

make graphene a suitable material for biosensing applications.

fascinated the attention of the scientific community worldwide.

Research-based on graphene oxide (GO) and graphene is an established interdisciplinary field associated with different disciplines such as physics, chemistry, material sciences, and nanotechnology with still a lot of emerging ideas to be developed. The result of working experience on other carbon allotropes leads to rapid discoveries of exceptional electronic, optical, and mechanical properties of graphene. In particular, its extraordinary charge carrier mobilities, thermal, and electrical conductivity, collective with high transparency and mechanical strength

These exceptional physicochemical properties indicate its potential for delivering new tactics and critical developments in electrochemical sciences. For instance, a large number of analytic molecules can be attached to the large surface of electrically conductive graphene sheets leading to the development of the highly sensitive miniaturized device. Direct electron transfer between graphene and redox species creates new prospects for sensing applications. Consequently, graphene has lately

GO is considered as a precursor for obtaining graphene via chemical or thermal reduction methods. It consists of single-layer graphite oxide, having various oxygencontaining groups, whose structure has been proposed through several models over the years [16–20]. Oxygen functional groups have been identified as typically in the form of hydroxyl, epoxy groups and carboxy, carbonyl, phenol, lactone, quinone on the basal plane, and at the sheet edges, respectively [21–23]. However, due to ambiguity pertaining to the nature and distribution of the oxygen-containing functional groups (**Figure 1**) [24, 25], its nonstoichiometric atomic composition, and the absence of adequately sensitive analytical techniques for GO characterization, its precise structure cannot be fully elucidated. The difference between GO and pristine graphene is as a result oxygenated groups present in GO which affect its electronic, mechanical, and electrochemical properties. Hence, they account for the differences between GO and pristine graphene [26]. The covalent oxygenated functional groups in GO give rise to remarkable structure defects, which are associated

*A schematic illustration of methods for the preparation of graphene, GO, and rGO by means of mechanical cleavage, exfoliation, CVD, and reduction methods including chemical, thermal, and electrochemical methods* 

*from graphite. Reprinted with permission from Ref. [25], Published by Elsevier.*

*DOI: http://dx.doi.org/10.5772/intechopen.93538*

**1.1 Graphene and graphene oxide**

### *Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments DOI: http://dx.doi.org/10.5772/intechopen.93538*

Research-based on graphene oxide (GO) and graphene is an established interdisciplinary field associated with different disciplines such as physics, chemistry, material sciences, and nanotechnology with still a lot of emerging ideas to be developed. The result of working experience on other carbon allotropes leads to rapid discoveries of exceptional electronic, optical, and mechanical properties of graphene. In particular, its extraordinary charge carrier mobilities, thermal, and electrical conductivity, collective with high transparency and mechanical strength make graphene a suitable material for biosensing applications.

These exceptional physicochemical properties indicate its potential for delivering new tactics and critical developments in electrochemical sciences. For instance, a large number of analytic molecules can be attached to the large surface of electrically conductive graphene sheets leading to the development of the highly sensitive miniaturized device. Direct electron transfer between graphene and redox species creates new prospects for sensing applications. Consequently, graphene has lately fascinated the attention of the scientific community worldwide.

### **1.1 Graphene and graphene oxide**

*Nanotechnology and the Environment*

pyrethrin, and pyrethroids compound. The unnecessary consumption of those agrochemicals has undesirable effects on the ecosystem, including a decreased population of beneficial insects as well as risks to vulnerable species and bird habitats. Pesticide pollution is becoming one of the most severe challenges of common public health around the globe because of their particular application in the agriculture sector to assure crop yield and productivity [6]. In some cases, acute poisoning may occur because of inappropriate handling that ultimately causes adverse health effects because of long-term and low-level exposures. The widespread diffusion of such toxic chemicals adversely affects a great part of the population. A large number of people, categorized by different patterns, ages, and degrees of exposure, are at increased risk to the adverse effects of these chemicals. Workers who are involved in the manufacturing and application of pesticides are at a considerable risk of exposure, which typically occurs among specific users in public health. In the agricultural sector, farmers may get direct exposure to pesticides during spraying across the agricultural fields [7, 8]. In the general population, individuals may be at a risk of pesticide exposure on a daily basis in food and drinking water or to pesticide drift in domestic areas adjacent to spraying areas [9]. Given their hazardous effect on human health and the environment, the prime concern should be of their rapid and reliable detection by a convenient method. Although various laboratory-based analytical methods such as colorimetry, capillary electrophoresis (CE), thin-layer chromatography (TLC), gas-liquid chromatography(GLC), high-performance liquid chromatography (HPLC), nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and enzyme-linked immunosorbent assays (ELISA) have been employed so far, but these suffer from one and the other drawback such as the use of expensive instrumentation, time-consuming process, and requirement of trained personnel [5]. Therefore, there is a dire need to develop sensitive, rapid, economically feasible, and easy-to-use methods for the detection of these compounds in the environment. Such efficient detection methods could be developed using biosensors that are used in a variety of applications for prompt and accurate detection of different analytes such as biomolecules and chemical compounds [10]. Various nanomaterials are generally categorized into nanoparticles, nanotubes, and nanocomposites, which can be generally employed for the diagnosis, degradation, and adsorption of chemical pesticides. Carbon nanomaterials or nanoparticles (NPs) have specific characteristics, including a high surface-to-volume ratio, good electrical conductivity, catalytic action, and beneficial biocompatibility and can be simply modified with functional groups, which has made them be often used in

pesticide biosensors to boost analytical efficiency [11].

It is well known that graphite and diamond are its most common allotropic form of carbon found in nature. Graphite, which is found as a natural mineral,

through weak attraction forces such as van der Waals forces. Single-layer out of these carbon atomic layers are packed in a two-dimensional honeycomb structure called as "graphene" termed coined by Boehm et al. [12]. It remains almost impossible to isolate graphene monolayer for several decades before Geim and Novoselov [13] who reported a scotch tape method or micromechanical cleavage method for the isolation of graphene monolayer from silicon oxide substrate. Discovery of graphene monolayer awarded Geim and Novoselov the Nobel Prize in Physics "for groundbreaking experiments regarding the two-dimensional

Graphene, which consists of a one-atom-thick planar sheet comprising an


hybridized carbon atomic layers that are stacked collectively

**130**

sp2

consists of sp2

material graphene".

science [14, 15].

GO is considered as a precursor for obtaining graphene via chemical or thermal reduction methods. It consists of single-layer graphite oxide, having various oxygencontaining groups, whose structure has been proposed through several models over the years [16–20]. Oxygen functional groups have been identified as typically in the form of hydroxyl, epoxy groups and carboxy, carbonyl, phenol, lactone, quinone on the basal plane, and at the sheet edges, respectively [21–23]. However, due to ambiguity pertaining to the nature and distribution of the oxygen-containing functional groups (**Figure 1**) [24, 25], its nonstoichiometric atomic composition, and the absence of adequately sensitive analytical techniques for GO characterization, its precise structure cannot be fully elucidated. The difference between GO and pristine graphene is as a result oxygenated groups present in GO which affect its electronic, mechanical, and electrochemical properties. Hence, they account for the differences between GO and pristine graphene [26]. The covalent oxygenated functional groups in GO give rise to remarkable structure defects, which are associated

### **Figure 1.**

*A schematic illustration of methods for the preparation of graphene, GO, and rGO by means of mechanical cleavage, exfoliation, CVD, and reduction methods including chemical, thermal, and electrochemical methods from graphite. Reprinted with permission from Ref. [25], Published by Elsevier.*

with some loss in its electrical conductivity [27], limiting the direct application of GO in electrically active materials and devices. In contrast, these functional groups can also be proved advantageous for exploiting GO in numerous other applications. The presence of polar oxygen-containing moieties gives GO a hydrophilic character making it dispersible in many solvents particularly in water [24, 28, 29]. Subsequent stable GO suspension can be used for preparing thin conducting films using spin coating, drop-casting, or spraying methods [23] for further to be used as electrodes.

Furthermore, well-known chemistry strategies can be used for the functionalization of GO using oxygen-containing groups as a site for chemical modification, which subsequently can be exploited for immobilization of various electroactive species via covalent or noncovalent bonds different application in sensing or catalysis. Thus, the physicochemical properties of GO can be tuned very easily by engineering its chemical composition [21, 30, 31].

Hydroxyl, epoxy, and carboxyl groups present in GO are covalently bonded to the carbon atom with sp3 hybridization are termed as oxidized region, disrupting the extended sp2 conjugated network of honeycomb lattice in graphene, which can be viewed as an unoxidized region [32, 33]. sp3 hybridized carbon clusters with oxygen-containing groups are uniformly but randomly distributed either above or below the GO plane [34]. Various microscopic and spectroscopic techniques have been employed for an in-depth analysis of the structure of GO. For instance, atomic force microscopy (AFM) provides the apparent thickness of the single-layer GO sheet beside the number of layers present [33, 35–37].

In contrast, conductive AFM demonstrates electrical defects found in GO [38]. Lately, one of the significant breakthroughs in determining the structure of GO, high-resolution transmission electron microscopy (HRTEM) has been employed for direct imaging of lattice atoms and topological defects present in single layer of GO [39–41]. Erickson et al. [39] identified specific atomic scale topographies of the GO monolayers, consisting of three major portions *viz.* holes, graphitic regions, and high-contrast disordered regions having approximate area percentages of 2, 16, and 82%, respectively.

According to the author, excessive oxidation and sheet exfoliation lead to the release of CO and CO2 consequently forming holes in GO. They also proposed that graphitic regions are a result of incomplete oxidation of basal plane having the preserved honeycomb structure of graphene, whereas the disordered region is rich in oxygen functionalities, such as hydroxyl, epoxides, and carbonyls with no order between them.

The chemical composition of GO and its oxygenated functionalities have been recognized through various spectroscopic techniques, which include solid-state nuclear magnetic resonance (SSNMR) [42–44], X-ray absorption near-edge spectroscopy (XANES) [45–49], Raman spectroscopy [45–49], X-ray photoelectron spectroscopy (XPS) [49] and Fourier transform infrared spectroscopy (FT-IR) [47, 50, 51]. Three main peaks around 60, 70, and 130 ppm are assigned to carbon atoms bonding to the epoxy group, hydroxyl group, and graphitic sp2 carbon, respectively [44], can be seen in a typical solid-state 13C magic-angle spinning NMR spectra of GO. Furthermore, three small additional peaks were also found at about 101, 167, and 191 ppm tentatively attributed to lactol, the ester carbonyl, and the ketone groups, correspondingly. XANES is another powerful tool for GO characterization, which provides information related to the degree of bond hybridization in mixed sp2 /sp3 -bonded carbon, the specific bonding arrangements of functional atoms, and graphitic crystal structure's degree of alignment inside GO [49].

Besides, Raman and FTIR spectroscopy data support the presence of oxygenated species in GO and its degree of oxidation. Raman spectrum of a GO displays two characteristic bands namely a D-band at ∼1340 cm−1 and G-band at ∼1580 cm−1 [52].

**133**

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments*

order scattering from the doubly degenerate E2g phonon modes of graphite whereas the D peak originates from structural imperfections and disorders produced by the addition of oxygenated groups on the carbon basal plane [52–54]. Hence, the intensity ratio of the D- and G-bands (Id/Ig) points to the oxidation degree, disorders, and the


Specific 2D structure and the presence of oxygenated functionalities are respon-

carbon. Generally, pristine GO films are insulating in nature

sible for excellent properties of GO, which include electronic, optical, thermal, mechanical, and electrochemical properties along with chemical reactivity. Electronic properties like conductivity of GO sheets are dependent on its chemical and atomic structure; in particular, the degree of oxidation arises from disorders

with an energy gap in electron density of states, [55] as well as sheet resistance (Rs) about 1012 Ω sq.−1 or higher [56]. This inherent insulating nature of GO is

barriers, leading to the lack or interruption of penetrating pathways among the sp2 carbon clusters. However, reduction of GO, whether chemical or thermal assists the transport of carriers, [57] helps to bring Rs down to several orders of magnitude and transforming the material into a semiconductor or finally into graphenelike material [58–60]. Reduced GO has conductivity up to ∼1000 S/m, [61] and activation energy as 32 ± 5 kcal/mol, estimated by the use of resistivity and temperature-programmed desorption (TPD) measurements [62]. Additionally, GO exhibits unique optical properties photoluminescence (PL) [63] occurring near-UV-to-blue visible (vis) to near-infrared (IR) wavelength range. Applications of this property have been sought in biosensing, fluorescence tags, and optoelec-

GO also demonstrates excellent electrocatalytic properties [66–68], such as the electrocatalytic activity of GO toward oxygen reduction and certain biomolecules [66], oxidation of hydrazine by reduced GO [67]. In addition to this, GO is capable of showing high electrochemical capacitance for application in ultracapacitors [68, 69]. As compared to carbon nanotubes, reduced GO exhibit higher electrochemical capacitance and cycling durability, wherever specific capacitance for reduced GO and carbon

The chemical reactivity of GO can be attributed to the presence of oxygenated functionalities and its disordered structure with defects. The reduction is the most important chemical reaction of GO, and it has been reduced by employing various approaches such as hydrazine, [70] sodium borohydride, [71] or hydroquinone, [72] in the liquid phase and the vapor phase using hydrazine/hydrogen [33, 52] or just by thermal annealing [52] or by using electrochemical techniques [73]. Chemical functionalization is another important chemical reaction involving GO, which includes the addition of other chemical groups to GO employing different chemical reactions. Oxygenated functionalities over GO surface play a very important role in its chemical reactions. Hence, it becomes an ideal approach to selectively chemical functionalize GO by utilizing reactions on these functionalities. Typically, covalent functionalization of GO can be realized using small molecules and polymers via activation, amidation, or esterification of either hydroxyls or carboxyl groups through coupling reactions [74–76]. For example, GO was made soluble in organic

nanotubes was found to be ∼165 and ∼86 F/g, respectively [68].

decrease in Id/Ig ratio was observed after thermal reduction, indicating a considerable regaining of conjugation in the graphitic structure after the defunctionalization of GO [45]. Functional groups can be recognized by the use of FT-IR spectroscopy and in the case of GO, it has reinforced the presence of hydroxyl (broad peak at 3050–3800 cm−1), carbonyl (1750–1850 cm−1), carboxyl (1650–1750 cm−1), C═C (1500–1600 cm−1), and



C▬O bonding, which acts as transport

*DOI: http://dx.doi.org/10.5772/intechopen.93538*

The G-band is a distinctive peak of all sp2

ring clusters in a matrix of sp3

ether or epoxide (1000–1280 cm−1) groups [43, 47, 50].

strongly associated with the amount of sp3

size of sp2

due to substantial sp3

tronic applications [64, 65].

### *Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments DOI: http://dx.doi.org/10.5772/intechopen.93538*

The G-band is a distinctive peak of all sp2 -hybridized carbon networks and due to firstorder scattering from the doubly degenerate E2g phonon modes of graphite whereas the D peak originates from structural imperfections and disorders produced by the addition of oxygenated groups on the carbon basal plane [52–54]. Hence, the intensity ratio of the D- and G-bands (Id/Ig) points to the oxidation degree, disorders, and the size of sp2 ring clusters in a matrix of sp3 - and sp2 -bonded carbon [53]. A significant decrease in Id/Ig ratio was observed after thermal reduction, indicating a considerable regaining of conjugation in the graphitic structure after the defunctionalization of GO [45]. Functional groups can be recognized by the use of FT-IR spectroscopy and in the case of GO, it has reinforced the presence of hydroxyl (broad peak at 3050–3800 cm−1), carbonyl (1750–1850 cm−1), carboxyl (1650–1750 cm−1), C═C (1500–1600 cm−1), and ether or epoxide (1000–1280 cm−1) groups [43, 47, 50].

Specific 2D structure and the presence of oxygenated functionalities are responsible for excellent properties of GO, which include electronic, optical, thermal, mechanical, and electrochemical properties along with chemical reactivity. Electronic properties like conductivity of GO sheets are dependent on its chemical and atomic structure; in particular, the degree of oxidation arises from disorders due to substantial sp3 carbon. Generally, pristine GO films are insulating in nature with an energy gap in electron density of states, [55] as well as sheet resistance (Rs) about 1012 Ω sq.−1 or higher [56]. This inherent insulating nature of GO is strongly associated with the amount of sp3 C▬O bonding, which acts as transport barriers, leading to the lack or interruption of penetrating pathways among the sp2 carbon clusters. However, reduction of GO, whether chemical or thermal assists the transport of carriers, [57] helps to bring Rs down to several orders of magnitude and transforming the material into a semiconductor or finally into graphenelike material [58–60]. Reduced GO has conductivity up to ∼1000 S/m, [61] and activation energy as 32 ± 5 kcal/mol, estimated by the use of resistivity and temperature-programmed desorption (TPD) measurements [62]. Additionally, GO exhibits unique optical properties photoluminescence (PL) [63] occurring near-UV-to-blue visible (vis) to near-infrared (IR) wavelength range. Applications of this property have been sought in biosensing, fluorescence tags, and optoelectronic applications [64, 65].

GO also demonstrates excellent electrocatalytic properties [66–68], such as the electrocatalytic activity of GO toward oxygen reduction and certain biomolecules [66], oxidation of hydrazine by reduced GO [67]. In addition to this, GO is capable of showing high electrochemical capacitance for application in ultracapacitors [68, 69]. As compared to carbon nanotubes, reduced GO exhibit higher electrochemical capacitance and cycling durability, wherever specific capacitance for reduced GO and carbon nanotubes was found to be ∼165 and ∼86 F/g, respectively [68].

The chemical reactivity of GO can be attributed to the presence of oxygenated functionalities and its disordered structure with defects. The reduction is the most important chemical reaction of GO, and it has been reduced by employing various approaches such as hydrazine, [70] sodium borohydride, [71] or hydroquinone, [72] in the liquid phase and the vapor phase using hydrazine/hydrogen [33, 52] or just by thermal annealing [52] or by using electrochemical techniques [73]. Chemical functionalization is another important chemical reaction involving GO, which includes the addition of other chemical groups to GO employing different chemical reactions. Oxygenated functionalities over GO surface play a very important role in its chemical reactions. Hence, it becomes an ideal approach to selectively chemical functionalize GO by utilizing reactions on these functionalities. Typically, covalent functionalization of GO can be realized using small molecules and polymers via activation, amidation, or esterification of either hydroxyls or carboxyl groups through coupling reactions [74–76]. For example, GO was made soluble in organic

*Nanotechnology and the Environment*

the carbon atom with sp3

the extended sp2

82%, respectively.

between them.

engineering its chemical composition [21, 30, 31].

be viewed as an unoxidized region [32, 33]. sp3

sheet beside the number of layers present [33, 35–37].

with some loss in its electrical conductivity [27], limiting the direct application of GO in electrically active materials and devices. In contrast, these functional groups can also be proved advantageous for exploiting GO in numerous other applications. The presence of polar oxygen-containing moieties gives GO a hydrophilic character making it dispersible in many solvents particularly in water [24, 28, 29]. Subsequent stable GO suspension can be used for preparing thin conducting films using spin coating, drop-casting, or spraying methods [23] for further to be used as electrodes. Furthermore, well-known chemistry strategies can be used for the functionalization of GO using oxygen-containing groups as a site for chemical modification, which subsequently can be exploited for immobilization of various electroactive species via covalent or noncovalent bonds different application in sensing or catalysis. Thus, the physicochemical properties of GO can be tuned very easily by

Hydroxyl, epoxy, and carboxyl groups present in GO are covalently bonded to

oxygen-containing groups are uniformly but randomly distributed either above or below the GO plane [34]. Various microscopic and spectroscopic techniques have been employed for an in-depth analysis of the structure of GO. For instance, atomic force microscopy (AFM) provides the apparent thickness of the single-layer GO

In contrast, conductive AFM demonstrates electrical defects found in GO [38]. Lately, one of the significant breakthroughs in determining the structure of GO, high-resolution transmission electron microscopy (HRTEM) has been employed for direct imaging of lattice atoms and topological defects present in single layer of GO [39–41]. Erickson et al. [39] identified specific atomic scale topographies of the GO monolayers, consisting of three major portions *viz.* holes, graphitic regions, and high-contrast disordered regions having approximate area percentages of 2, 16, and

According to the author, excessive oxidation and sheet exfoliation lead to the release of CO and CO2 consequently forming holes in GO. They also proposed that graphitic regions are a result of incomplete oxidation of basal plane having the preserved honeycomb structure of graphene, whereas the disordered region is rich in oxygen functionalities, such as hydroxyl, epoxides, and carbonyls with no order

The chemical composition of GO and its oxygenated functionalities have been recognized through various spectroscopic techniques, which include solid-state nuclear magnetic resonance (SSNMR) [42–44], X-ray absorption near-edge

spectroscopy (XANES) [45–49], Raman spectroscopy [45–49], X-ray photoelectron spectroscopy (XPS) [49] and Fourier transform infrared spectroscopy (FT-IR) [47, 50, 51]. Three main peaks around 60, 70, and 130 ppm are assigned to carbon

respectively [44], can be seen in a typical solid-state 13C magic-angle spinning NMR spectra of GO. Furthermore, three small additional peaks were also found at about 101, 167, and 191 ppm tentatively attributed to lactol, the ester carbonyl, and the ketone groups, correspondingly. XANES is another powerful tool for GO characterization, which provides information related to the degree of bond hybridization

Besides, Raman and FTIR spectroscopy data support the presence of oxygenated species in GO and its degree of oxidation. Raman spectrum of a GO displays two characteristic bands namely a D-band at ∼1340 cm−1 and G-band at ∼1580 cm−1 [52].


atoms bonding to the epoxy group, hydroxyl group, and graphitic sp2

atoms, and graphitic crystal structure's degree of alignment inside GO [49].

hybridization are termed as oxidized region, disrupting

hybridized carbon clusters with

carbon,

conjugated network of honeycomb lattice in graphene, which can

**132**

in mixed sp2

/sp3

solvents by rendering a coupling reaction with octadecylamine via amide formation, where carboxyl functionalities of GO were first activated by SOCl2 [74]. Ringopening reactions can be used to functionalize epoxy groups by nucleophilic attack at α-carbon by the amine [77]. For example, octadecylamine attachment to GO surface [57], attachment of an amine group-containing ionic liquid through ringopening reaction with epoxy groups on GO [77] making chemically functionalized GO more soluble in water as well as other organic solvents.

Noncovalent functionalization of GO is also known in addition to covalent modifications. Noncovalent modification of GO can be accomplished by various forces and interactions including hydrogen bonding, van der Walls interaction, π-π stacking, cation-π interaction [78, 79]. Doxorubicin hydrochloride (Dox)/GO hybrid was synthesized through noncovalent interactions using π-π stacking and hydrophobic interactions between the sp2 carbon matrix and quinone functionality of Dox as primary noncovalent interactions. Additionally, strong hydrogen bonding between hydroxyl and amine groups of Dox with hydroxyl and carboxyl groups of GO also helps in covalent modification [78].

The usefulness of GO can be estimated from this fact that along with its applications in electronics and displays, it can also act as a carbocatalyst for assisting hydration and oxidation reactions [80–82]. GO can be used as a catalyst for oxidation of alcohols and alkenes besides hydration of alkynes into aldehydes and ketones [80]. Furthermore, GO has a broad range of oxidation reaction, for example, it can oxidize olefins to diones, methylbenzene to aldehydes as well as other dehydrogenations [83].

### **2. Graphene oxide-based nanohybrids**

GO and reduced GO (rGO) themselves have many advantageous properties, but a substantial amount of work is being done to utilize these materials in combination with other nanomaterials such as nanoparticles or polymers. Based on their morphologies, graphene oxide/nanoparticle nanohybrids can be roughly divided into two classes: first where nanoparticles are grown or decorated upon sheets of GO and second, nanoparticles are wrapped in GO sheets. Particularly in the first type, graphene/nanoparticle nanohybrid can be synthesized by combining GO or rGO with different nanoparticles such as metal nanoparticles, metal oxide nanoparticles, quantum dots, or silica nanoparticles depending upon the application desired. A unique combination of the nanoparticles and GO/rGO makes a novel synergistic nanomaterial with enhanced and diverse properties. For example, decorated metal or metal oxide nanoparticles over GO surface modify the local electronic structure and hence the charge transfer behavior of graphene [84] resulting in improved catalytic behavior of this nanocomposite. Alternatively, enhancement in sensitivity and selectivity has been observed in sensors derived from the combination of graphene material and nanoparticles having good conductivity and catalytic behavior [85, 86].

Similarly, in graphene oxide/polymer nanohybrids, surface functionalities present on GO surface groups can assist the combination of GO with polymers or synthesis of the polymer by different polymerization techniques [87, 88]. A typical modification strategy includes covalent bonding, that is, "Grafting to" and "Grafting from" approaches, whereas noncovalent modification includes π-π stacking, electrostatic interaction, and hydrogen bonding [89–91]. Similarly, fabrication strategies of graphene oxide/polymer nanohybrids synthesis include in situ polymerization, melt compounding, latex blending, solution mixing, and electro polymerization [92, 93].

**135**

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments*

**3. Synthetic methodologies for graphene oxide/nanoparticle** 

Graphene oxide/nanoparticle nanohybrids in which GO/rGO sheets are decorated with nanoparticles having dimensions ranging from few nanometers to a couple of hundred nanometers [94] can be attained by attaching different types of nanoparticles to the surface of GO sheets either by in situ method or by ex situ method. In situ method comprises growing nanoparticles on the surface of GO; however, in the case of ex situ method, pre-synthesized nanoparticles are immobilized over the surface of GO. The presence of defects and oxygenated functionalities makes GO an encouraging templates for the attachment, nucleation, and growth numerous metal (e.g., Au [87, 95], Ag [96], Pt [97], etc.) and metal oxide nanoparticles (e.g., Fe3O4 [98], TiO2 [99], ZnO [100], SnO2 [101], Cu2O [102, 103], MnO2 [104], NiO [105, 106], La2O3, [107, 108], etc.). Subsequent graphene oxide/ nanoparticle nanohybrid offers several unique and beneficial properties for various applications depending on individual characteristics showed by nanoparticles

The following section includes the different methods for the preparation of graphene oxide/nanoparticles nanocomposites, for example, chemical reduction, hydrothermal route, and electrochemical method or ex situ synthesis, while primarily focusing on individual characteristics and advantages of each technique correlated to the properties of resulting graphene oxide/nanoparticle

Graphene oxide/metal nanoparticle nanohybrids are mostly synthesized by chemical reduction of their metal salt precursors such as HAuCl4, AgNO3, and K2PtCl4 utilizing reducing agents such as sodium citrate, ethylene glycol or polyethylene glycol, and sodium borohydride [96, 109], positively charged metallic salts get nucleated on negatively charged functional groups of GO which results in the growth of metal nanoparticles on its surface, while reducing GO to rGO, preserving the excellent electrical properties of rGO. Moreover, the density of metal nanoparticles can also be controlled by tuning the density of oxygenated

Chemical reduction technique is the most basic method for the preparation of Graphene oxide/noble metal nanoparticle nanohybrids. In particular, gold (AuNP) and silver nanoparticles (AgNPs) are among the most comprehensively studied nanomaterials with a wide range of biomedical applications such as diagnostics, imaging, drug delivery [110]. High biocompatibility and surface plasmon resonance are some of the very unique properties of noble nanoparticles making them of particular interest. These properties can be tuned to desired values according to the shape and size of the nanoparticles [111]. Furthermore, graphene oxide/noble metal nanoparticle nanohybrids are able to show SERS in addition to enhanced catalytic activity [112]. Reduced graphene oxide/AuNPs are the most common and utilized nanocomposites, which can be prepared by mixing HAuCl4 with GO and sodium citrate, followed by reduction using NaBH4 to form AuNPs while reducing GO to rGO [113, 114]. Similarly, instead of using HAuCl4, AgNO3 is used for reduced graphene oxide/AgNPs composite synthesis [112, 114]. In a similar way, reduced graphene oxide/platinum nanoparticle or reduced graphene oxide/palladium nanoparticle nanohybrids are formed by mixing graphene oxide with chloroplatinic acid (H2PtCl6) or tetrachloropalladic acid (H2PdCl4), followed by reduction with

*DOI: http://dx.doi.org/10.5772/intechopen.93538*

**nanohybrids**

immobilized upon GO.

functionalities on GO.

ethylene glycol or any other reducing agent.

**3.1 Chemical reduction method**

nanohybrids.

### **3. Synthetic methodologies for graphene oxide/nanoparticle nanohybrids**

Graphene oxide/nanoparticle nanohybrids in which GO/rGO sheets are decorated with nanoparticles having dimensions ranging from few nanometers to a couple of hundred nanometers [94] can be attained by attaching different types of nanoparticles to the surface of GO sheets either by in situ method or by ex situ method. In situ method comprises growing nanoparticles on the surface of GO; however, in the case of ex situ method, pre-synthesized nanoparticles are immobilized over the surface of GO. The presence of defects and oxygenated functionalities makes GO an encouraging templates for the attachment, nucleation, and growth numerous metal (e.g., Au [87, 95], Ag [96], Pt [97], etc.) and metal oxide nanoparticles (e.g., Fe3O4 [98], TiO2 [99], ZnO [100], SnO2 [101], Cu2O [102, 103], MnO2 [104], NiO [105, 106], La2O3, [107, 108], etc.). Subsequent graphene oxide/ nanoparticle nanohybrid offers several unique and beneficial properties for various applications depending on individual characteristics showed by nanoparticles immobilized upon GO.

The following section includes the different methods for the preparation of graphene oxide/nanoparticles nanocomposites, for example, chemical reduction, hydrothermal route, and electrochemical method or ex situ synthesis, while primarily focusing on individual characteristics and advantages of each technique correlated to the properties of resulting graphene oxide/nanoparticle nanohybrids.

### **3.1 Chemical reduction method**

*Nanotechnology and the Environment*

solvents by rendering a coupling reaction with octadecylamine via amide formation, where carboxyl functionalities of GO were first activated by SOCl2 [74]. Ringopening reactions can be used to functionalize epoxy groups by nucleophilic attack at α-carbon by the amine [77]. For example, octadecylamine attachment to GO surface [57], attachment of an amine group-containing ionic liquid through ringopening reaction with epoxy groups on GO [77] making chemically functionalized

Noncovalent functionalization of GO is also known in addition to covalent modifications. Noncovalent modification of GO can be accomplished by various forces and interactions including hydrogen bonding, van der Walls interaction, π-π stacking, cation-π interaction [78, 79]. Doxorubicin hydrochloride (Dox)/GO hybrid was synthesized through noncovalent interactions using π-π stacking and

of Dox as primary noncovalent interactions. Additionally, strong hydrogen bonding between hydroxyl and amine groups of Dox with hydroxyl and carboxyl groups of

GO and reduced GO (rGO) themselves have many advantageous properties, but a substantial amount of work is being done to utilize these materials in combination with other nanomaterials such as nanoparticles or polymers. Based on their morphologies, graphene oxide/nanoparticle nanohybrids can be roughly divided into two classes: first where nanoparticles are grown or decorated upon sheets of GO and second, nanoparticles are wrapped in GO sheets. Particularly in the first type, graphene/nanoparticle nanohybrid can be synthesized by combining GO or rGO with different nanoparticles such as metal nanoparticles, metal oxide nanoparticles, quantum dots, or silica nanoparticles depending upon the application desired. A unique combination of the nanoparticles and GO/rGO makes a novel synergistic nanomaterial with enhanced and diverse properties. For example, decorated metal or metal oxide nanoparticles over GO surface modify the local electronic structure and hence the charge transfer behavior of graphene [84] resulting in improved catalytic behavior of this nanocomposite. Alternatively, enhancement in sensitivity and selectivity has been observed in sensors derived from the combination of graphene material and nanoparticles having good

Similarly, in graphene oxide/polymer nanohybrids, surface functionalities present on GO surface groups can assist the combination of GO with polymers or synthesis of the polymer by different polymerization techniques [87, 88]. A typical modification strategy includes covalent bonding, that is, "Grafting to" and "Grafting from" approaches, whereas noncovalent modification includes π-π stacking, electrostatic interaction, and hydrogen bonding [89–91]. Similarly, fabrication strategies of graphene oxide/polymer nanohybrids synthesis include in situ polymerization, melt compounding, latex blending, solution mixing, and electro

The usefulness of GO can be estimated from this fact that along with its applications in electronics and displays, it can also act as a carbocatalyst for assisting hydration and oxidation reactions [80–82]. GO can be used as a catalyst for oxidation of alcohols and alkenes besides hydration of alkynes into aldehydes and ketones [80]. Furthermore, GO has a broad range of oxidation reaction, for example, it can oxidize olefins to diones, methylbenzene to aldehydes as well as

carbon matrix and quinone functionality

GO more soluble in water as well as other organic solvents.

hydrophobic interactions between the sp2

GO also helps in covalent modification [78].

**2. Graphene oxide-based nanohybrids**

conductivity and catalytic behavior [85, 86].

other dehydrogenations [83].

**134**

polymerization [92, 93].

Graphene oxide/metal nanoparticle nanohybrids are mostly synthesized by chemical reduction of their metal salt precursors such as HAuCl4, AgNO3, and K2PtCl4 utilizing reducing agents such as sodium citrate, ethylene glycol or polyethylene glycol, and sodium borohydride [96, 109], positively charged metallic salts get nucleated on negatively charged functional groups of GO which results in the growth of metal nanoparticles on its surface, while reducing GO to rGO, preserving the excellent electrical properties of rGO. Moreover, the density of metal nanoparticles can also be controlled by tuning the density of oxygenated functionalities on GO.

Chemical reduction technique is the most basic method for the preparation of Graphene oxide/noble metal nanoparticle nanohybrids. In particular, gold (AuNP) and silver nanoparticles (AgNPs) are among the most comprehensively studied nanomaterials with a wide range of biomedical applications such as diagnostics, imaging, drug delivery [110]. High biocompatibility and surface plasmon resonance are some of the very unique properties of noble nanoparticles making them of particular interest. These properties can be tuned to desired values according to the shape and size of the nanoparticles [111]. Furthermore, graphene oxide/noble metal nanoparticle nanohybrids are able to show SERS in addition to enhanced catalytic activity [112]. Reduced graphene oxide/AuNPs are the most common and utilized nanocomposites, which can be prepared by mixing HAuCl4 with GO and sodium citrate, followed by reduction using NaBH4 to form AuNPs while reducing GO to rGO [113, 114]. Similarly, instead of using HAuCl4, AgNO3 is used for reduced graphene oxide/AgNPs composite synthesis [112, 114]. In a similar way, reduced graphene oxide/platinum nanoparticle or reduced graphene oxide/palladium nanoparticle nanohybrids are formed by mixing graphene oxide with chloroplatinic acid (H2PtCl6) or tetrachloropalladic acid (H2PdCl4), followed by reduction with ethylene glycol or any other reducing agent.

### **3.2 Hydrothermal methods**

Another very common method for synthesizing inorganic nanoparticles is the hydrothermal method. This method gives nanoparticles with high crystallinity and narrow size distribution over graphene oxide. Moreover, there is no need for postannealing or calcination for reduced graphene oxide/metal nanoparticle nanohybrids. In general, the growth of nanocrystals is induced by high temperature and pressure, which is also responsible for the conversion of GO to rGO during the process. However, in most cases reducing agents are also added to make sure a complete reduction of GO [115].

The most common nanohybrids synthesized by the hydrothermal method are reduced graphene oxide/ metal oxide nanoparticle nanohybrids which include ZnO [116], TiO2 [117], Fe3O4 [118], SnO2 [119], etc.

Reduced graphene oxide/metal oxide nanoparticle hybrids illustrate their specific properties such as higher capacitance, which depends upon nanoparticle size, shape, and crystallinity; also, it helps in the suppression of restacking and agglomeration in graphene oxide sheets. Furthermore, these nanocomposites also exhibit enhancement in electron conductivity, high surface area as compared to GO or graphene, also shortened route for ion transfer, which in all responsible for their higher electrochemical activity. For instance, reduced graphene oxide/SnO2 nanosphere nanohybrid exhibited significantly enhanced formaldehyde sensing performance compared to the pristine SnO2 nanospheres [119]. Alternatively, reduced graphene oxide/magnetic nanoparticle nanohybrid has been prepared using FeCl3 as an iron source and ethylene glycol as a reducing agent [120]. Resulting nanohybrid displayed outstanding electrical conductivity as well as magnetic properties. Similarly, chalcogenide quantum dots, for example, CdS [121], ZnS [122], Cu2S [123], and MoS2 [124], etc. have been successfully immobilized on graphene oxide exploiting hydrothermal methods.

### **3.3 Electrochemical deposition method**

The electrochemical deposition method is a very simple, low cost, fast, easy to miniaturize, highly stable, reproducible, and green technique for preparation of graphene oxide/nanoparticle composite [125]. The advantage of this technique is that the size and shape of the nanoparticles to be deposited can be precisely controlled using varying the conditions of electrochemical deposition. Electrochemical deposition methods have been established for the fabrication of a vast variety of graphene oxide/ metal nanoparticle composites for noble metals like Au, [126] using cyclic voltammetry (CV), which helped in fabricating an electrode for the determination of trace amount As(III) employing square wave anodic stripping voltammetry, Ag, [127] for carrying out the oxidation of different amino acids such as glycine, alanine, leucine, aspartic and glutamic acids using cyclic voltammetry and amperometric techniques. Similarly for Pt [128], Pt nanoparticles embedded rGO on glassy carbon electrode are utilized to carry out electrooxidation of formic acid. Generally, a typical electrochemical deposition experiment is consisting of three basic steps, that is, assembly of graphene oxide sheets on the electrode, graphene oxide-coated electrode immersion in an electrolytic solution of selected metal precursors, and potential applied across electrodes. A majority of research has concentrated on using electrochemical deposition methods for synthesizing graphene oxide/metal nanoparticle composite, but there are some reports for preparation of graphene oxide/metal oxide nanoparticle composite synthesis by the same technique. For instance, Cl-doped n-type Cu2O nanoparticles with a direct band gap of ca. 2.0 eV [128] have been deposited on rGO electrodes with a subsequent carrier concentration of up to 1 × 1020 cm−3 [129].

**137**

sors are discussed.

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments*

902 mAh g−1 after 100 cycles at 300 mA g−1 when used as the electrode.

**4. Graphene oxide-based nanohybrids as pesticide biosensors**

An analytical device that utilizes a biological sensing element to detect a specific analyte molecule or family of the analytical molecule is called as biosensor. Biosensors can seek applications in diverse fields such as food safety, environmental monitoring, and biomedical field. Generally, biosensors are consisting of two basic parts: first receptor, any organic or inorganic material that interacts with analytes. The second part, a transducer, which converts a recognition event, happened between analyte and receptor, into a measurable signal. Evaluation of biosensor 's performance is measured by its sensitivity to target, linear range, the limit of detection, dynamic ranges, reproducibility, precision in response, and selectivity [139]. Other parameters that are also important include the sensor's response time, ease of use, portability, storage, and operational stability. Graphene oxide/nanoparticle nanohybrids are known to be well suited for application in biosensing because of the rise of new advantageous properties due to the combination of graphene oxide and nanoparticles. Here, in this section, a detailed aspect of graphene oxide nanohybrid-based biosensors, specifically electrochemical biosen-

Flexible and 2D sheet-like structure of graphene oxide and its derivatives help in wrapping or encapsulating nanoparticles in the range from 100 nm to few

GO and rGO sheets are most commonly used for nanoparticle encapsulation due to their hydrophilic nature and ease of fabrication. Noncovalent bonds are responsible for this type of encapsulation; for instance, modification of nanoparticle surface with a positive charge is used for electrostatic interaction with negatively charged GO [130, 131]. Encapsulation of a variety of nanomaterials, for example, polymer, inorganic nanoparticles, metal, and metal oxide nanoparticles, can be achieved by controlling the cracked size of GO and rGO, thus obtained composite offer enhanced properties and additional advantages. For example, enhancement in electrical, optical, and electrochemical properties has been observed for graphene oxide encapsulated nanoparticles, also suppression of aggregation of small nanoparticles [132, 133]. Moreover, leaching of nanoparticles is reduced in graphene oxide encapsulated nanoparticles due to the high amount of contact between GO and nanoparticles, making them more stable. Several reports have revealed the encapsulation of metal oxide nanoparticles with graphene oxide. For example, rGO encapsulated cobalt oxide nanoparticles have shown a very high reversible capacity (1000 mAh g−1) over 130 cycles, much more than the normal cobalt oxide nanoparticles used for capacitors [131]. Moreover, rGO encapsulated Co3O4 nanofibersbased sensor exhibited an excellent sensitivity with a fast response and recovery to different concentrations of ammonia from 5 to 100 ppm at room temperature [134]. Furthermore, a nonenzymatic electrochemical sensor based on 3D porous phase graphene oxide sheets encapsulated chalcopyrite (GOS@CuFeS2) nanocomposite is reported for the detection of methyl paraoxon [135]. Encapsulation of nonconducting silicon oxide nanoparticles within conducting rGO can be used as the "bridgingmaterial" in a field-effect transistor-based biosensor [130, 136]. Similarly, Si nanoparticles encapsulated with rGO via electrostatic interaction using APTES has also been reported [137, 138], resulting in less destruction and aggregation of SiNPs as compared to pristine nanoparticles. It also exhibited a high reversible capacity of

*DOI: http://dx.doi.org/10.5772/intechopen.93538*

micrometers.

**3.4 Graphene oxide/encapsulated nanoparticles**

### **3.4 Graphene oxide/encapsulated nanoparticles**

*Nanotechnology and the Environment*

**3.2 Hydrothermal methods**

reduction of GO [115].

[116], TiO2 [117], Fe3O4 [118], SnO2 [119], etc.

exploiting hydrothermal methods.

**3.3 Electrochemical deposition method**

Another very common method for synthesizing inorganic nanoparticles is the hydrothermal method. This method gives nanoparticles with high crystallinity and narrow size distribution over graphene oxide. Moreover, there is no need for postannealing or calcination for reduced graphene oxide/metal nanoparticle nanohybrids. In general, the growth of nanocrystals is induced by high temperature and pressure, which is also responsible for the conversion of GO to rGO during the process. However, in most cases reducing agents are also added to make sure a complete

The most common nanohybrids synthesized by the hydrothermal method are reduced graphene oxide/ metal oxide nanoparticle nanohybrids which include ZnO

Reduced graphene oxide/metal oxide nanoparticle hybrids illustrate their specific properties such as higher capacitance, which depends upon nanoparticle size, shape, and crystallinity; also, it helps in the suppression of restacking and agglomeration in graphene oxide sheets. Furthermore, these nanocomposites also exhibit enhancement in electron conductivity, high surface area as compared to GO or graphene, also shortened route for ion transfer, which in all responsible for their higher electrochemical activity. For instance, reduced graphene oxide/SnO2 nanosphere nanohybrid exhibited significantly enhanced formaldehyde sensing performance compared to the pristine SnO2 nanospheres [119]. Alternatively, reduced graphene oxide/magnetic nanoparticle nanohybrid has been prepared using FeCl3 as an iron source and ethylene glycol as a reducing agent [120]. Resulting nanohybrid displayed outstanding electrical conductivity as well as magnetic properties. Similarly, chalcogenide quantum dots, for example, CdS [121], ZnS [122], Cu2S [123], and MoS2 [124], etc. have been successfully immobilized on graphene oxide

The electrochemical deposition method is a very simple, low cost, fast, easy to miniaturize, highly stable, reproducible, and green technique for preparation of graphene oxide/nanoparticle composite [125]. The advantage of this technique is that the size and shape of the nanoparticles to be deposited can be precisely controlled using varying the conditions of electrochemical deposition. Electrochemical deposition methods have been established for the fabrication of a vast variety of graphene oxide/ metal nanoparticle composites for noble metals like Au, [126] using cyclic voltammetry (CV), which helped in fabricating an electrode for the determination of trace amount As(III) employing square wave anodic stripping voltammetry, Ag, [127] for carrying out the oxidation of different amino acids such as glycine, alanine, leucine, aspartic and glutamic acids using cyclic voltammetry and amperometric techniques. Similarly for Pt [128], Pt nanoparticles embedded rGO on glassy carbon electrode are utilized to carry out electrooxidation of formic acid. Generally, a typical electrochemical deposition experiment is consisting of three basic steps, that is, assembly of graphene oxide sheets on the electrode, graphene oxide-coated electrode immersion in an electrolytic solution of selected metal precursors, and potential applied across electrodes. A majority of research has concentrated on using electrochemical deposition methods for synthesizing graphene oxide/metal nanoparticle composite, but there are some reports for preparation of graphene oxide/metal oxide nanoparticle composite synthesis by the same technique. For instance, Cl-doped n-type Cu2O nanoparticles with a direct band gap of ca. 2.0 eV [128] have been deposited on rGO electrodes with a subsequent carrier concentration of up to 1 × 1020 cm−3 [129].

**136**

Flexible and 2D sheet-like structure of graphene oxide and its derivatives help in wrapping or encapsulating nanoparticles in the range from 100 nm to few micrometers.

GO and rGO sheets are most commonly used for nanoparticle encapsulation due to their hydrophilic nature and ease of fabrication. Noncovalent bonds are responsible for this type of encapsulation; for instance, modification of nanoparticle surface with a positive charge is used for electrostatic interaction with negatively charged GO [130, 131]. Encapsulation of a variety of nanomaterials, for example, polymer, inorganic nanoparticles, metal, and metal oxide nanoparticles, can be achieved by controlling the cracked size of GO and rGO, thus obtained composite offer enhanced properties and additional advantages. For example, enhancement in electrical, optical, and electrochemical properties has been observed for graphene oxide encapsulated nanoparticles, also suppression of aggregation of small nanoparticles [132, 133]. Moreover, leaching of nanoparticles is reduced in graphene oxide encapsulated nanoparticles due to the high amount of contact between GO and nanoparticles, making them more stable. Several reports have revealed the encapsulation of metal oxide nanoparticles with graphene oxide. For example, rGO encapsulated cobalt oxide nanoparticles have shown a very high reversible capacity (1000 mAh g−1) over 130 cycles, much more than the normal cobalt oxide nanoparticles used for capacitors [131]. Moreover, rGO encapsulated Co3O4 nanofibersbased sensor exhibited an excellent sensitivity with a fast response and recovery to different concentrations of ammonia from 5 to 100 ppm at room temperature [134]. Furthermore, a nonenzymatic electrochemical sensor based on 3D porous phase graphene oxide sheets encapsulated chalcopyrite (GOS@CuFeS2) nanocomposite is reported for the detection of methyl paraoxon [135]. Encapsulation of nonconducting silicon oxide nanoparticles within conducting rGO can be used as the "bridgingmaterial" in a field-effect transistor-based biosensor [130, 136]. Similarly, Si nanoparticles encapsulated with rGO via electrostatic interaction using APTES has also been reported [137, 138], resulting in less destruction and aggregation of SiNPs as compared to pristine nanoparticles. It also exhibited a high reversible capacity of 902 mAh g−1 after 100 cycles at 300 mA g−1 when used as the electrode.

### **4. Graphene oxide-based nanohybrids as pesticide biosensors**

An analytical device that utilizes a biological sensing element to detect a specific analyte molecule or family of the analytical molecule is called as biosensor. Biosensors can seek applications in diverse fields such as food safety, environmental monitoring, and biomedical field. Generally, biosensors are consisting of two basic parts: first receptor, any organic or inorganic material that interacts with analytes. The second part, a transducer, which converts a recognition event, happened between analyte and receptor, into a measurable signal. Evaluation of biosensor 's performance is measured by its sensitivity to target, linear range, the limit of detection, dynamic ranges, reproducibility, precision in response, and selectivity [139]. Other parameters that are also important include the sensor's response time, ease of use, portability, storage, and operational stability. Graphene oxide/nanoparticle nanohybrids are known to be well suited for application in biosensing because of the rise of new advantageous properties due to the combination of graphene oxide and nanoparticles. Here, in this section, a detailed aspect of graphene oxide nanohybrid-based biosensors, specifically electrochemical biosensors are discussed.

Electrochemical sensors are the largest group of sensors for detecting or analyzing various molecules by directly converting biological recognition event into an electrical signal. A typical electrochemical biosensor is composed of a threeelectrode system with a working electrode consisting of a biological recognition element, counter electrode, and reference electrode separated by suitable electrolytes. Based on their biological recognition process, electrochemical biosensors can be divided into two main groups: first, affinity-based sensors, and second, catalytic sensors. The basic principle of working in affinity biosensors is the measurable electric signal that arises due to the interaction of the biological component like an antibody, enzyme, nucleic acid, or a receptor and target molecules. Whereas in catalytic sensors, incorporated nanoparticles or enzymes recognize the analyte molecules and produce an electroactive species by catalysis. The electrical signal produced by the electroactive species is then correlated to the concentration of the target analyte molecule. Commonly used techniques in electrochemical biosensing include different forms of voltammetry (e.g., cyclic, linear sweep, differential, square wave, etc.) and amperometry [139].

The large surface area of graphene oxide nanohybrids is beneficial for the immobilization of biomolecules to use it as a platform for biosensing material. Furthermore, the synergistic effect of graphene oxide also enhances achievable sensitivities and measurable ranges. Most commonly biomolecule immobilized biosensors utilize enzymes, antibodies, and DNA as biomolecules.

Lately, enzyme immobilized GO nanohybrids-based biosensors have fascinated a lot for the detection of various kinds of analytes. The most common example is the determination of glucose, which has an important role in the diagnosis and therapy of diabetes. Apart from glucose oxidase based biosensors, other enzyme-based biosensors are also known with high sensitivity and selectivity, which includes biosensors based on alcohol dehydrogenase [140], microperoxidase [141], horseradish peroxidase [142], tyrosinase [143], urease [144], and acetylcholinesterase [145]. Acetylcholinesterase (AChE) is a catalytic enzyme present in the central nervous system, which catalyzes the hydrolysis of acetylcholine and choline esters. Its catalytic ability is severely affected by the presence of different types of organophosphorus and carbamate pesticides even in trace amounts. AChE can be easily immobilized on the surface of graphene oxide-based nanohybrids which offer a large surface area and abundant active sites so that they can be used for developing AChE inhibition-based biosensors [146].

Although a lot of work has already been reported on graphene-based biosensors; however, due to novel microbes and diseases associated with them, excess use of toxicants in food and feed products, nonjudicial use of pesticide and day by day disintegrating environmental conditions urgently need tools for detection of such chemicals and biologicals, and hence, more rapid and urgent requirement for the development of biosensors arises In the past 2 years, countless new graphene oxide nanohybrids-based biosensors are reported. For example, Yao et al. [147] reported an electrochemical biosensor based on the inhibition of AChE, using a gold nanocage/graphene oxide-chitosan nanocomposite-modified screen-printed carbon electrode for detection of chlorpyrifos (**Figure 2**). Where the biosensor showed good electrocatalytic activity for the oxidation of enzymatically produced thiocholine and detected chlorpyrifos concentrations as low as 3 ng L−1.

Similarly, Bao et al. [148] developed a biosensor for malathion detection based on three-dimensional graphene-copper oxide nanoflowers nanocomposites electrode, and the group was able to obtain a wide linear relationship to malathion concentration ranging from 3pM to 46.665nM with a theoretical limit of detection at 0.92pM. Moreover, Cui et al. reported a very stable electrochemical AChE biosensor for detection of dichlorvos by adsorption of AChE on chitosan, TiO2 sol-gel,

**139**

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments*

and rGO-based many fold matrix, with the linear range varying from 0.036 μM to 22.6 μM, limit of detection of 29 nM and total time for detection about 25 min. Furthermore, electrochemical acetylcholinesterase biosensor based on the silver nanowire, graphene, TiO2 sol-gel, chitosan, and acetylcholinesterase is fabricated

*(a) A schematic diagram of the construction process of AChE biosensor based on screen-printed electrodes, (b) and (c) DPV behavior, and percent inhibition obtained by biosensor in the presence of chlorpyrifos. Reprinted with permission from ref. [147], published by the Royal Society of Chemistry (RSC) on behalf of* 

the second linear range was observed between 10−9 and 10−4 M.

*the Centre National de la Recherche Scientifique (CNRS) and the RSC.*

12.3–10,000 nmol L−1 and limit of detection as 3.7 nmol L−1.

On a similar note, Zhang et al. [150] developed a highly sensitive AChE amperometric biosensor based on conjugated polymer and Ag-rGO-NH2 nanocomposite. Group used a slightly different method for electrode fabrication where authors first electrochemically polymerized 4, 7-di (furan-2-yl) benzothiadiazole on electrode surface followed by deposition of Ag-rGO-NH2 nanocomposite. The biosensor is found to be biocompatible with high efficiency having the linear range from 0.099 to 9.9 μg L−1 0.032 μg L−1 for malathion and 0.001 μg L−1 for trichlorfon. Moreover, Mogha et al. [151] developed a biosensor for the detection of Chlorpyrifos using rGO supported Zirconium Oxide immobilized AChE (**Figure 4**). The group is able to detect the Chlorpyrifos in two linear ranges first from 10−13 to 10−9 M, whereas

Aghaie et al. [152] developed a nonenzymatic biosensor for the detection of paraoxon ethyl. A graphene-based NiFe bimetallic phosphosulfide nanocomposite biosensor is fabricated, where square wave voltammetric is used as a detection technique. The linear range for the detection of paraoxon methyl is found to be

Furthermore, a group of Hondred et al. [153] (**Figure 5**) utilized salt impregnated inkjet maskless lithography for preparation of 3D porous architectured graphene for application in biosensing of paraoxon and supercapacitor. The as developed biosensor showed a wide linear range from 10 to 500 nM, low limit of

*DOI: http://dx.doi.org/10.5772/intechopen.93538*

by Zhang et al. [149] (**Figure 3**).

**Figure 2.**

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments DOI: http://dx.doi.org/10.5772/intechopen.93538*

**Figure 2.**

*Nanotechnology and the Environment*

square wave, etc.) and amperometry [139].

AChE inhibition-based biosensors [146].

Electrochemical sensors are the largest group of sensors for detecting or analyzing various molecules by directly converting biological recognition event into an electrical signal. A typical electrochemical biosensor is composed of a threeelectrode system with a working electrode consisting of a biological recognition element, counter electrode, and reference electrode separated by suitable electrolytes. Based on their biological recognition process, electrochemical biosensors can be divided into two main groups: first, affinity-based sensors, and second, catalytic sensors. The basic principle of working in affinity biosensors is the measurable electric signal that arises due to the interaction of the biological component like an antibody, enzyme, nucleic acid, or a receptor and target molecules. Whereas in catalytic sensors, incorporated nanoparticles or enzymes recognize the analyte molecules and produce an electroactive species by catalysis. The electrical signal produced by the electroactive species is then correlated to the concentration of the target analyte molecule. Commonly used techniques in electrochemical biosensing include different forms of voltammetry (e.g., cyclic, linear sweep, differential,

The large surface area of graphene oxide nanohybrids is beneficial for the immobilization of biomolecules to use it as a platform for biosensing material. Furthermore, the synergistic effect of graphene oxide also enhances achievable sensitivities and measurable ranges. Most commonly biomolecule immobilized

Lately, enzyme immobilized GO nanohybrids-based biosensors have fascinated a lot for the detection of various kinds of analytes. The most common example is the determination of glucose, which has an important role in the diagnosis and therapy of diabetes. Apart from glucose oxidase based biosensors, other enzyme-based biosensors are also known with high sensitivity and selectivity, which includes biosensors based on alcohol dehydrogenase [140], microperoxidase [141], horseradish peroxidase [142], tyrosinase [143], urease [144], and acetylcholinesterase [145]. Acetylcholinesterase (AChE) is a catalytic enzyme present in the central nervous system, which catalyzes the hydrolysis of acetylcholine and choline esters. Its catalytic ability is severely affected by the presence of different types of organophosphorus and carbamate pesticides even in trace amounts. AChE can be easily immobilized on the surface of graphene oxide-based nanohybrids which offer a large surface area and abundant active sites so that they can be used for developing

Although a lot of work has already been reported on graphene-based biosensors; however, due to novel microbes and diseases associated with them, excess use of toxicants in food and feed products, nonjudicial use of pesticide and day by day disintegrating environmental conditions urgently need tools for detection of such chemicals and biologicals, and hence, more rapid and urgent requirement for the development of biosensors arises In the past 2 years, countless new graphene oxide nanohybrids-based biosensors are reported. For example, Yao et al. [147] reported an electrochemical biosensor based on the inhibition of AChE, using a gold nanocage/graphene oxide-chitosan nanocomposite-modified screen-printed carbon electrode for detection of chlorpyrifos (**Figure 2**). Where the biosensor showed good electrocatalytic activity for the oxidation of enzymatically produced thiocho-

Similarly, Bao et al. [148] developed a biosensor for malathion detection based on three-dimensional graphene-copper oxide nanoflowers nanocomposites electrode, and the group was able to obtain a wide linear relationship to malathion concentration ranging from 3pM to 46.665nM with a theoretical limit of detection at 0.92pM. Moreover, Cui et al. reported a very stable electrochemical AChE biosensor for detection of dichlorvos by adsorption of AChE on chitosan, TiO2 sol-gel,

biosensors utilize enzymes, antibodies, and DNA as biomolecules.

line and detected chlorpyrifos concentrations as low as 3 ng L−1.

**138**

*(a) A schematic diagram of the construction process of AChE biosensor based on screen-printed electrodes, (b) and (c) DPV behavior, and percent inhibition obtained by biosensor in the presence of chlorpyrifos. Reprinted with permission from ref. [147], published by the Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.*

and rGO-based many fold matrix, with the linear range varying from 0.036 μM to 22.6 μM, limit of detection of 29 nM and total time for detection about 25 min. Furthermore, electrochemical acetylcholinesterase biosensor based on the silver nanowire, graphene, TiO2 sol-gel, chitosan, and acetylcholinesterase is fabricated by Zhang et al. [149] (**Figure 3**).

On a similar note, Zhang et al. [150] developed a highly sensitive AChE amperometric biosensor based on conjugated polymer and Ag-rGO-NH2 nanocomposite. Group used a slightly different method for electrode fabrication where authors first electrochemically polymerized 4, 7-di (furan-2-yl) benzothiadiazole on electrode surface followed by deposition of Ag-rGO-NH2 nanocomposite. The biosensor is found to be biocompatible with high efficiency having the linear range from 0.099 to 9.9 μg L−1 0.032 μg L−1 for malathion and 0.001 μg L−1 for trichlorfon. Moreover, Mogha et al. [151] developed a biosensor for the detection of Chlorpyrifos using rGO supported Zirconium Oxide immobilized AChE (**Figure 4**). The group is able to detect the Chlorpyrifos in two linear ranges first from 10−13 to 10−9 M, whereas the second linear range was observed between 10−9 and 10−4 M.

Aghaie et al. [152] developed a nonenzymatic biosensor for the detection of paraoxon ethyl. A graphene-based NiFe bimetallic phosphosulfide nanocomposite biosensor is fabricated, where square wave voltammetric is used as a detection technique. The linear range for the detection of paraoxon methyl is found to be 12.3–10,000 nmol L−1 and limit of detection as 3.7 nmol L−1.

Furthermore, a group of Hondred et al. [153] (**Figure 5**) utilized salt impregnated inkjet maskless lithography for preparation of 3D porous architectured graphene for application in biosensing of paraoxon and supercapacitor. The as developed biosensor showed a wide linear range from 10 to 500 nM, low limit of

### **Figure 3.**

*(a) Schematic illustration of the AChE based biosensor and its working mechanism to ATCl.(b) and (c) SEM images of Gra/AgNWs/SiO2 nanohybrids, where large graphene sheet is enhancing the connection with AgNWs in (b) with small graphene pieces further improving the performance of biosensor (in red rectangle shown in (c)), while (d) and (e) represent the inhibition of AChE in presence of DDVP using the biosensors. Reprinted with permission from ref [149], Published by The Royal Society of Chemistry.*

### **Figure 4.**

*An illustration of rGO supported Zirconium Oxide immobilized AChE nanohybrid as a biosensing platform for chlorpyrifos detection. Reprinted with permission from Ref. [151], published by Elsevier.*

detection of 0.6 nM with high sensitivity of 12.4 nA nM−1; moreover as a supercapacitor, it demonstrates a high energy density of 0.25 mW h cm−3 at a power density of 0.3 W cm−3. Similarly, another AChE biosensor is developed based on a film of gold nanoparticles/three-dimensional graphene, by Dong et al. [154], for methyl parathion and malathion detection in a linear range from 1.0 × 10−10 to 1.0 × 10−6 g L−1, having limits of detection as 2.78 × 10−11 g L−1 and 2.17 × 10−11 g L−1.

Some more examples of biosensors based on graphene oxide nanohybrids for the detection of different types of pesticides such as methyl parathion [155–158], carbofuran [155, 157, 159], chlorpyrifos [156], imidacloprid [160], phoxim with graphene/GCE [161], poly(3-methylthiophene)/nitrogen-doped graphene [162], and carboxylic chitosan /silver nanoclusters-rGO [163], paraoxon and chlorpyrifos with TiO2-GO/UiO-66 composite [164], carbaryl with MWCNTs/GO nanoribbons [165], carbaryl and chlorpyrifos with AgNPs-CGR/NF composite [166],

**141**

**Figure 5.**

*Chemistry.*

AuNPs-graphene nanosheets [176].

**5. Conclusion and future aspects**

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments*

chlorpyrifos and carbofuran with ZnONPs-CGR/NF composite [167], carbaryl and monocrotophos with ionic liquid-functionalized graphene /gelatin [168], monocrotophos with Prussian blue nanocubes [169], malathion and carbaryl with rGO-AuNP/β-cyclodextrin/Prussian blue-CS nanocomposites [170], fenitrothion with cerium oxide nanoparticle-decorated rGO [171], diuron with rGO-AuNPs [172], paraoxon-ethyl with rGO-AuNPs/polypyrrole [173], carbaryl with Graphene/ polyaniline nanohybrid [174], carbaryl with an electrochemically induced porous GO network [175], and methyl parathion and malathion with plant esterase—Chit/

*(a) Schematic diagram of AChE biosensor portraying the functionalization approach for pesticide detection using EDC/NHS. (b) AChE pesticides biosensor characterization with photograph, activity, sensitivity, and comparison between salt impregnated inkjet maskless lithography (SIIML) and inkjet maskless lithography (IML)-based biosensors. Reprinted with permission from Ref. [153], published by The Royal Society of* 

Graphene oxide is an attractive material that has gathered ever accumulative interest from the scientific community over the past several years. Owing to its

*DOI: http://dx.doi.org/10.5772/intechopen.93538*

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments DOI: http://dx.doi.org/10.5772/intechopen.93538*

**Figure 5.**

*Nanotechnology and the Environment*

**140**

**Figure 3.**

**Figure 4.**

detection of 0.6 nM with high sensitivity of 12.4 nA nM−1; moreover as a supercapacitor, it demonstrates a high energy density of 0.25 mW h cm−3 at a power density of 0.3 W cm−3. Similarly, another AChE biosensor is developed based on a film of gold nanoparticles/three-dimensional graphene, by Dong et al. [154], for methyl parathion and malathion detection in a linear range from 1.0 × 10−10 to 1.0 × 10−6 g L−1, having limits of detection as 2.78 × 10−11 g L−1 and 2.17 × 10−11 g L−1. Some more examples of biosensors based on graphene oxide nanohybrids for the detection of different types of pesticides such as methyl parathion [155–158], carbofuran [155, 157, 159], chlorpyrifos [156], imidacloprid [160], phoxim with graphene/GCE [161], poly(3-methylthiophene)/nitrogen-doped graphene [162], and carboxylic chitosan /silver nanoclusters-rGO [163], paraoxon and chlorpyrifos with TiO2-GO/UiO-66 composite [164], carbaryl with MWCNTs/GO nanoribbons [165], carbaryl and chlorpyrifos with AgNPs-CGR/NF composite [166],

*for chlorpyrifos detection. Reprinted with permission from Ref. [151], published by Elsevier.*

*An illustration of rGO supported Zirconium Oxide immobilized AChE nanohybrid as a biosensing platform* 

*(a) Schematic illustration of the AChE based biosensor and its working mechanism to ATCl.(b) and (c) SEM images of Gra/AgNWs/SiO2 nanohybrids, where large graphene sheet is enhancing the connection with AgNWs in (b) with small graphene pieces further improving the performance of biosensor (in red rectangle shown in (c)), while (d) and (e) represent the inhibition of AChE in presence of DDVP using the biosensors. Reprinted* 

*with permission from ref [149], Published by The Royal Society of Chemistry.*

*(a) Schematic diagram of AChE biosensor portraying the functionalization approach for pesticide detection using EDC/NHS. (b) AChE pesticides biosensor characterization with photograph, activity, sensitivity, and comparison between salt impregnated inkjet maskless lithography (SIIML) and inkjet maskless lithography (IML)-based biosensors. Reprinted with permission from Ref. [153], published by The Royal Society of Chemistry.*

chlorpyrifos and carbofuran with ZnONPs-CGR/NF composite [167], carbaryl and monocrotophos with ionic liquid-functionalized graphene /gelatin [168], monocrotophos with Prussian blue nanocubes [169], malathion and carbaryl with rGO-AuNP/β-cyclodextrin/Prussian blue-CS nanocomposites [170], fenitrothion with cerium oxide nanoparticle-decorated rGO [171], diuron with rGO-AuNPs [172], paraoxon-ethyl with rGO-AuNPs/polypyrrole [173], carbaryl with Graphene/ polyaniline nanohybrid [174], carbaryl with an electrochemically induced porous GO network [175], and methyl parathion and malathion with plant esterase—Chit/ AuNPs-graphene nanosheets [176].

### **5. Conclusion and future aspects**

Graphene oxide is an attractive material that has gathered ever accumulative interest from the scientific community over the past several years. Owing to its

extraordinary properties, graphene oxide and its derivatives are already being exploited in a wide variety of applications comprising electronics, energy, biosensors, catalysis, green chemistry, etc. Though, in the last decade, the relentless search for new opportunities benefiting from graphene oxide has led to the introduction and evolution of graphene oxide-based nanohybrids, which combine matchless and beneficial properties of nanomaterials/nanotechnology with those of graphene oxide to yield valuable and synergistic effects.

In this chapter, we have discussed the brief history of graphene oxide and graphene, emphasizing the structural details of graphene oxide and excellent properties associated with it. Graphene oxide-based nanohybrids show the synergistic effect of having properties of both graphene oxide as well as other constituting material whether nanoparticle or polymer. Synthetic mythologies of graphene oxide-based nanohybrids have also been discussed here in this chapter, in particular, graphene oxide/nanoparticle nanohybrids. Finally, applications of graphene oxide-based nanohybrids were presented in the field of biosensors and catalysis. In the case of biosensors, the main emphasis was given to the largest class of biosensors, that is, electrochemical biosensors, which consist of mainly enzyme biosensors and electrochemical DNA sensors, but some cases of other electrochemical sensors were also demonstrate. Applications of these graphene oxide-based hybrids in catalysis were also discussed emphasizing their use as an organic reaction catalyst, photocatalysts for the degradation of environmentally harmful molecules.

In conclusion, we have highlighted the properties of graphene oxide-based nanohybrids wherein these nanostructures can bring excellent synergistic advantages to a wide variety of biosensing applications. While promising, the field of graphene oxide-based nanohybrids is still not completely exhausted and several intriguing issues must be resolved before its maximum potential can be achieved. Besides, we envision that the evolution of this technology will result in the use of graphene oxide-based nanohybrids in a much wider range of applications by employing high quality and large-scale fabrication of these materials to minimize the cost leading to their commercialization. We also hope that this chapter has motivated attention from various disciplines that will gain benefits from the expansion of graphene oxide-based nanohybrids development for applications in numerous other fields of interest.

### **Acknowledgements**

The author is heartily thankful to the Director, Shriram Institute for Industrial Research and Monica Singh, In-charge, Pesticide Laboratory for unconditional help and support.

**143**

**Author details**

Navin Kumar Mogha

Industrial Research, Delhi, India

provided the original work is properly cited.

Pesticide Laboratory, Analytical Science Division-Biology, Shriram Institute for

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

\*Address all correspondence to: navinmogha@gmail.com

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments*

*DOI: http://dx.doi.org/10.5772/intechopen.93538*

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments DOI: http://dx.doi.org/10.5772/intechopen.93538*

### **Author details**

*Nanotechnology and the Environment*

oxide to yield valuable and synergistic effects.

for the degradation of environmentally harmful molecules.

extraordinary properties, graphene oxide and its derivatives are already being exploited in a wide variety of applications comprising electronics, energy, biosensors, catalysis, green chemistry, etc. Though, in the last decade, the relentless search for new opportunities benefiting from graphene oxide has led to the introduction and evolution of graphene oxide-based nanohybrids, which combine matchless and beneficial properties of nanomaterials/nanotechnology with those of graphene

In this chapter, we have discussed the brief history of graphene oxide and graphene, emphasizing the structural details of graphene oxide and excellent properties associated with it. Graphene oxide-based nanohybrids show the synergistic effect of having properties of both graphene oxide as well as other constituting material whether nanoparticle or polymer. Synthetic mythologies of graphene oxide-based nanohybrids have also been discussed here in this chapter, in particular, graphene oxide/nanoparticle nanohybrids. Finally, applications of graphene oxide-based nanohybrids were presented in the field of biosensors and catalysis. In the case of biosensors, the main emphasis was given to the largest class of biosensors, that is, electrochemical biosensors, which consist of mainly enzyme biosensors and electrochemical DNA sensors, but some cases of other electrochemical sensors were also demonstrate. Applications of these graphene oxide-based hybrids in catalysis were also discussed emphasizing their use as an organic reaction catalyst, photocatalysts

In conclusion, we have highlighted the properties of graphene oxide-based nanohybrids wherein these nanostructures can bring excellent synergistic advantages to a wide variety of biosensing applications. While promising, the field of graphene oxide-based nanohybrids is still not completely exhausted and several intriguing issues must be resolved before its maximum potential can be achieved. Besides, we envision that the evolution of this technology will result in the use of graphene oxide-based nanohybrids in a much wider range of applications by employing high quality and large-scale fabrication of these materials to minimize the cost leading to their commercialization. We also hope that this chapter has motivated attention from various disciplines that will gain benefits from the expansion of graphene oxide-based nanohybrids development for applications in numerous

The author is heartily thankful to the Director, Shriram Institute for Industrial Research and Monica Singh, In-charge, Pesticide Laboratory for unconditional help

**142**

other fields of interest.

**Acknowledgements**

and support.

Navin Kumar Mogha Pesticide Laboratory, Analytical Science Division-Biology, Shriram Institute for Industrial Research, Delhi, India

\*Address all correspondence to: navinmogha@gmail.com

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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[140] Pilas J, Selmer T, Keusgen M, Schöning MJ. Screen-printed carbon electrodes modified with graphene oxide for the design of a reagentfree NAD+-dependent biosensor array. Analytical Chemistry. 2019;**91**:15293-15299. DOI: 10.1021/acs. analchem.9b04481

[141] Xu M, Shen Y, Wang L, Gong C, Chen S. A novel H2O2 biosensor based on the composite of MP-11 encapasulated in PCN-333 (Al) graphene oxide. International Journal of Electrochemical Science. 2017;**12**:10390- 10401. DOI: 10.20964/2017.11.45

[142] López Marzo AM, Mayorga-Martinez CC, Pumera M. 3D-printed graphene direct electron transfer enzyme biosensors. Biosensors & Bioelectronics. 2020;**151**:111980. DOI: 10.1016/j.bios.2019.111980

[143] Hashim HS, Fen YW, Omar NAS, Daniyal WMEMM, Saleviter S, Abdullah J. Structural, optical and potential sensing properties of tyrosinase immobilized graphene oxide thin film on gold surface. Optik (Stuttg). 2020;**212**:164786. DOI: 10.1016/j.ijleo.2020.164786

[144] Chou JC, Wu CY, Liao YH, Lai CH, Yan SJ, Wu YX, et al. Enzymatic urea sensor based on graphene oxide/ titanium dioxide films modified by urease-magnetic beads. IEEE Transactions on Nanotechnology. 2019;**18**:336-344. DOI: 10.1109/ TNANO.2019.2907225

[145] Fenoy GE, Marmisollé WA, Azzaroni O, Knoll W. Acetylcholine biosensor based on the electrochemical functionalization of graphene fieldeffect transistors. Biosensors & Bioelectronics. 2020;**148**:111796. DOI: 10.1016/j.bios.2019.111796

[146] Krishnan SK, Singh E, Singh P, Meyyappan M, Nalwa HS. A review on graphene-based nanocomposites for electrochemical and fluorescent biosensors. RSC Advances. 2019;**9**: 8778-8781. DOI: 10.1039/c8ra09577a

[147] Yao Y, Wang G, Chu G, An X, Guo Y, Sun X. The development of a novel biosensor based on gold nanocages/graphene oxide-chitosan modified acetylcholinesterase for organophosphorus pesticide detection. New Journal of Chemistry. 2019;**43**:13816-13826. DOI: 10.1039/ c9nj02556a

[148] Bao J, Huang T, Wang Z, Yang H, Geng X, Xu G, et al. 3D graphene/ copper oxide nano-flowers based acetylcholinesterase biosensor for sensitive detection of organophosphate pesticides. Sensors and Actuators B: Chemical. 2019;**279**:95-101. DOI: 10.1016/j.snb.2018.09.118

[149] Zhang J, Wang B, Li Y, Shu W, Hu H, Yang L. An acetylcholinesterase biosensor with high stability and sensitivity based on silver nanowiregraphene-TiO2 for the detection of organophosphate pesticides. RSC Advances. 2019;**9**:25248-25256. DOI: 10.1039/c9ra02140j

[150] Zhang P, Sun T, Rong S, Zeng D, Yu H, Zhang Z, et al. A sensitive amperometric AChEbiosensor for organophosphate pesticides detection based on conjugated polymer and Ag-rGO-NH2 nanocomposite. Bioelectrochemistry. 2019;**127**:163-170. DOI: 10.1016/j. bioelechem.2019.02.003

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[157] Yang L, Zhou Q, Wang G, Yang Y. Acetylcholinesterase biosensor based on SnO2 nanoparticles-carboxylic graphene-nafion modified electrode for detection of pesticides. Biosensors & Bioelectronics. 2013;**49**:25-31. DOI:

talanta.2013.03.025

10.1016/j.bios.2013.04.037

Saraswathi R, Chen SM, Chen TW. Acetylcholinesterase biosensor for the detection of methyl parathion at an electrochemically reduced graphene oxide-nafion modified glassy carbon electrode. International Journal of Electrochemical Science. 2017;**12**: 4768-4781. DOI: 10.20964/2017.06.77

[159] Tan X, Hu Q, Wu J, Li X, Li P, Yu H, et al. Electrochemical sensor based on molecularly imprinted polymer reduced graphene oxide and gold nanoparticles modified electrode for detection of carbofuran. Sensors and Actuators B: Chemical. 2015;**220**:216-221. DOI: 10.1016/j.

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snb.2015.05.048

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s12161-014-9813-y

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[162] Wu L, Lei W, Han Z, Zhang Y, Xia M, Hao Q. A novel non-enzyme amperometric platform based on poly(3-methylthiophene)/nitrogen

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[151] Mogha NK, Sahu V, Sharma M, Sharma RK, Masram DT. Biocompatible

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s12161-019-01486-8

c8nh00377g

10.1039/c9ay00549h

10.1016/j.ab.2013.03.004

[153] Hondred JA, Medintz IL,

[154] Dong P, Jiang B, Zheng J. A novel acetylcholinesterase biosensor based on gold nanoparticles obtained by electroless plating on threedimensional graphene for detecting organophosphorus pesticides in water and vegetable samples. Analytical Methods. 2019;**11**:2428-2434. DOI:

[155] Yang L, Wang G, Liu Y. An acetylcholinesterase biosensor based on platinum nanoparticles- carboxylic graphene-nafion-modified electrode for detection of pesticides. Analytical Biochemistry. 2013;**437**:144-149. DOI:

[156] Yang L, Wang G, Liu Y, Wang M. Development of a biosensor based on immobilization of acetylcholinesterase on NiO nanoparticles–carboxylic graphene–nafion modified electrode for detection of pesticides. Talanta.

Claussen JC. Enhanced electrochemical biosensor and supercapacitor with 3D porous architectured graphene via salt impregnated inkjet maskless lithography. Nanoscale Horizons. 2019;**4**:735-746. DOI: 10.1039/

ZrO2- reduced graphene oxide immobilized AChE biosensor for chlorpyrifos detection. Materials and Design. 2016;**111**:312-320. DOI: 10.1016/j.matdes.2016.09.019

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[151] Mogha NK, Sahu V, Sharma M, Sharma RK, Masram DT. Biocompatible ZrO2- reduced graphene oxide immobilized AChE biosensor for chlorpyrifos detection. Materials and Design. 2016;**111**:312-320. DOI: 10.1016/j.matdes.2016.09.019

*Nanotechnology and the Environment*

[139] Ronkainen NJ, Halsall HB, Heineman WR. Electrochemical biosensors. Chemical Society Reviews. 2010;**39**:1747-1763. DOI: 10.1039/

[140] Pilas J, Selmer T, Keusgen M, Schöning MJ. Screen-printed carbon electrodes modified with graphene oxide for the design of a reagentfree NAD+-dependent biosensor array. Analytical Chemistry.

2019;**91**:15293-15299. DOI: 10.1021/acs.

[141] Xu M, Shen Y, Wang L, Gong C, Chen S. A novel H2O2 biosensor based on the composite of MP-11 encapasulated in PCN-333 (Al)-

graphene oxide. International Journal of Electrochemical Science. 2017;**12**:10390-

10401. DOI: 10.20964/2017.11.45

[142] López Marzo AM, Mayorga-Martinez CC, Pumera M. 3D-printed graphene direct electron transfer enzyme biosensors. Biosensors & Bioelectronics. 2020;**151**:111980. DOI:

[143] Hashim HS, Fen YW, Omar NAS, Daniyal WMEMM, Saleviter S, Abdullah J. Structural, optical and potential sensing properties of tyrosinase immobilized graphene oxide thin film on gold surface. Optik (Stuttg). 2020;**212**:164786. DOI: 10.1016/j.ijleo.2020.164786

[144] Chou JC, Wu CY, Liao YH, Lai CH, Yan SJ, Wu YX, et al. Enzymatic urea sensor based on graphene oxide/ titanium dioxide films modified by urease-magnetic beads. IEEE Transactions on Nanotechnology. 2019;**18**:336-344. DOI: 10.1109/

10.1016/j.bios.2019.111980

b714449k

analchem.9b04481

pulse-modulated induction thermal plasmas with intermittent feedstock feeding. Japanese Journal of Applied Physics. 2020;**59**:SHHE07. DOI: 10.35848/1347-4065/ab71db

[145] Fenoy GE, Marmisollé WA, Azzaroni O, Knoll W. Acetylcholine biosensor based on the electrochemical functionalization of graphene fieldeffect transistors. Biosensors & Bioelectronics. 2020;**148**:111796. DOI:

[146] Krishnan SK, Singh E, Singh P, Meyyappan M, Nalwa HS. A review on graphene-based nanocomposites for electrochemical and fluorescent biosensors. RSC Advances. 2019;**9**: 8778-8781. DOI: 10.1039/c8ra09577a

[147] Yao Y, Wang G, Chu G, An X, Guo Y, Sun X. The development of a novel biosensor based on gold nanocages/graphene oxide-chitosan modified acetylcholinesterase for organophosphorus pesticide detection. New Journal of Chemistry. 2019;**43**:13816-13826. DOI: 10.1039/

[148] Bao J, Huang T, Wang Z, Yang H, Geng X, Xu G, et al. 3D graphene/ copper oxide nano-flowers based acetylcholinesterase biosensor for sensitive detection of organophosphate pesticides. Sensors and Actuators B: Chemical. 2019;**279**:95-101. DOI:

10.1016/j.snb.2018.09.118

10.1039/c9ra02140j

[150] Zhang P, Sun T, Rong S, Zeng D, Yu H, Zhang Z, et al. A sensitive amperometric AChEbiosensor for organophosphate pesticides detection based on

bioelechem.2019.02.003

conjugated polymer and Ag-rGO-NH2 nanocomposite. Bioelectrochemistry. 2019;**127**:163-170. DOI: 10.1016/j.

[149] Zhang J, Wang B, Li Y, Shu W, Hu H, Yang L. An acetylcholinesterase biosensor with high stability and sensitivity based on silver nanowiregraphene-TiO2 for the detection of organophosphate pesticides. RSC Advances. 2019;**9**:25248-25256. DOI:

c9nj02556a

10.1016/j.bios.2019.111796

**154**

TNANO.2019.2907225

[152] Aghaie A, Khanmohammadi A, Hajian A, Schmid U, Bagheri H. Nonenzymatic electrochemical determination of paraoxon ethyl in water and fruits by graphene-based NiFe bimetallic phosphosulfide nanocomposite as a superior sensing layer. Food Analytical Methods. 2019;**12**:1545-1555. DOI: 10.1007/ s12161-019-01486-8

[153] Hondred JA, Medintz IL, Claussen JC. Enhanced electrochemical biosensor and supercapacitor with 3D porous architectured graphene via salt impregnated inkjet maskless lithography. Nanoscale Horizons. 2019;**4**:735-746. DOI: 10.1039/ c8nh00377g

[154] Dong P, Jiang B, Zheng J. A novel acetylcholinesterase biosensor based on gold nanoparticles obtained by electroless plating on threedimensional graphene for detecting organophosphorus pesticides in water and vegetable samples. Analytical Methods. 2019;**11**:2428-2434. DOI: 10.1039/c9ay00549h

[155] Yang L, Wang G, Liu Y. An acetylcholinesterase biosensor based on platinum nanoparticles- carboxylic graphene-nafion-modified electrode for detection of pesticides. Analytical Biochemistry. 2013;**437**:144-149. DOI: 10.1016/j.ab.2013.03.004

[156] Yang L, Wang G, Liu Y, Wang M. Development of a biosensor based on immobilization of acetylcholinesterase on NiO nanoparticles–carboxylic graphene–nafion modified electrode for detection of pesticides. Talanta.

2013;**113**:135-141. DOI: 10.1016/j. talanta.2013.03.025

[157] Yang L, Zhou Q, Wang G, Yang Y. Acetylcholinesterase biosensor based on SnO2 nanoparticles-carboxylic graphene-nafion modified electrode for detection of pesticides. Biosensors & Bioelectronics. 2013;**49**:25-31. DOI: 10.1016/j.bios.2013.04.037

[158] Jeyapragasam T,

Saraswathi R, Chen SM, Chen TW. Acetylcholinesterase biosensor for the detection of methyl parathion at an electrochemically reduced graphene oxide-nafion modified glassy carbon electrode. International Journal of Electrochemical Science. 2017;**12**: 4768-4781. DOI: 10.20964/2017.06.77

[159] Tan X, Hu Q, Wu J, Li X, Li P, Yu H, et al. Electrochemical sensor based on molecularly imprinted polymer reduced graphene oxide and gold nanoparticles modified electrode for detection of carbofuran. Sensors and Actuators B: Chemical. 2015;**220**:216-221. DOI: 10.1016/j. snb.2015.05.048

[160] Zhang M, Zhao HT, Xie TJ, Yang X, Dong AJ, Zhang H, et al. Molecularly imprinted polymer on graphene surface for selective and sensitive electrochemical sensing imidacloprid. Sensors and Actuators B: Chemical. 2017;**252**:991-1002. DOI: 10.1016/j. snb.2017.04.159

[161] Chao M, Chen M. Electrochemical determination of Phoxim in food samples employing a Graphene-modified glassy carbon electrode. Food Analytical Methods. 2014;**7**:1729-1736. DOI: 10.1007/ s12161-014-9813-y

[162] Wu L, Lei W, Han Z, Zhang Y, Xia M, Hao Q. A novel non-enzyme amperometric platform based on poly(3-methylthiophene)/nitrogen

doped graphene modified electrode for determination of trace amounts of pesticide phoxim. Sensors and Actuators B: Chemical. 2015;**206**:495-501. DOI: 10.1016/j.snb.2014.09.098

[163] Zheng Y, Wang A, Lin H, Fu L, Cai W. A sensitive electrochemical sensor for direct phoxim detection based on an electrodeposited reduced graphene oxide-gold nanocomposite. RSC Advances. 2015;**5**:15425-15430. DOI: 10.1039/c4ra15872e

[164] Karimian N, Fakhri H, Amidi S, Hajian A, Arduini F, Bagheri H. A novel sensing layer based on metal-organic framework UiO-66 modified with TiO2-graphene oxide: Application to rapid, sensitive and simultaneous determination of paraoxon and chlorpyrifos. New Journal of Chemistry. 2019;**43**:2600-2609. DOI: 10.1039/ c8nj06208k

[165] Liu Q, Fei A, Huan J, Mao H, Wang K. Effective amperometric biosensor for carbaryl detection based on covalent immobilization acetylcholinesterase on multiwall carbon nanotubes/graphene oxide nanoribbons nanostructure. Journal of Electroanalytical Chemistry. 2015;**740**:8-13. DOI: 10.1016/j. jelechem.2014.12.037

[166] Liu Y, Wang G, Li C, Zhou Q, Wang M, Yang L. A novel acetylcholinesterase biosensor based on carboxylic graphene coated with silver nanoparticles for pesticide detection. Materials Science and Engineering: C. 2014;**35**:253-258. DOI: 10.1016/j. msec.2013.10.036

[167] Wang G, Tan X, Zhou Q, Liu Y, Wang M, Yang L. Synthesis of highly dispersed zinc oxide nanoparticles on carboxylic graphene for development a sensitive acetylcholinesterase biosensor. Sensors and Actuators B: Chemical. 2014;**190**:730-736. DOI: 10.1016/j. snb.2013.09.042

[168] Zheng Y, Liu Z, Jing Y, Li J, Zhan H. An acetylcholinesterase biosensor based on ionic liquid functionalized graphenegelatin-modified electrode for sensitive detection of pesticides. Sensors and Actuators B: Chemical. 2015;**210**:389- 397. DOI: 10.1016/j.snb.2015.01.003

[169] Zhang L, Zhang A, Du D, Lin Y. Biosensor based on Prussian blue nanocubes/reduced graphene oxide nanocomposite for detection of organophosphorus pesticides. Nanoscale. 2012;**4**:4674-4679. DOI: 10.1039/c2nr30976a

[170] Zhao H, Ji X, Wang B, Wang N, Li X, Ni R, et al. An ultra-sensitive acetylcholinesterase biosensor based on reduced graphene oxide-Au nanoparticles-β-cyclodextrin/Prussian blue-chitosan nanocomposites for organophosphorus pesticides detection. Biosensors & Bioelectronics. 2015;**65**:23-30. DOI: 10.1016/j. bios.2014.10.007

[171] Ensafi AA, Noroozi R, Zandi-Atashbar N, Rezaei B. Cerium (IV) oxide decorated on reduced graphene oxide, a selective and sensitive electrochemical sensor for fenitrothion determination. Sensors actuators B Chem. 2017;**245**:980-987. DOI: 10.1016/j. snb.2017.01.186

[172] Shams N, Lim HN, Hajian R, Yusof NA, Abdullah J, Sulaiman Y, et al. A promising electrochemical sensor based on Au nanoparticles decorated reduced graphene oxide for selective detection of herbicide diuron in natural waters. Journal of Applied Electrochemistry. 2016;**46**:655-666. DOI: 10.1007/s10800-016-0950-4

[173] Yang Y, Asiri AM, Du D, Lin Y. Acetylcholinesterase biosensor based on a gold nanoparticlepolypyrrole-reduced graphene oxide nanocomposite modified electrode for the amperometric detection of organophosphorus pesticides. Analyst.

**157**

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments*

*DOI: http://dx.doi.org/10.5772/intechopen.93538*

2014;**139**:3055-3060. DOI: 10.1039/

[174] Li Y, Zhang Y, Han G, Xiao Y, Li M, Zhou W. An acetylcholinesterase

detection of pesticides. Chinese Journal of Chemistry. 2016;**34**:82-88. DOI:

[175] Li Y, Shi L, Han G, Xiao Y, Zhou W.

carbaryl based on acetylcholinesterase immobilized onto electrochemically inducing porous graphene oxide network. Sensors and Actuators B: Chemical. 2017;**238**:945-953. DOI:

biosensor based on graphene/ polyaniline composite film for

Electrochemical biosensing of

10.1002/cjoc.201500747

10.1016/j.snb.2016.07.152

jafc.5b03971

[176] Bao J, Hou C, Chen M, Li J, Huo D, Yang M, et al. Plant esterasechitosan/gold nanoparticles-graphene nanosheet composite-based biosensor for the ultrasensitive detection of organophosphate pesticides. Journal of Agricultural and Food Chemistry. 2015;**63**:10319-10326. DOI: 10.1021/acs.

c4an00068d

*Graphene Oxide-Based Nanohybrids as Pesticide Biosensors: Latest Developments DOI: http://dx.doi.org/10.5772/intechopen.93538*

2014;**139**:3055-3060. DOI: 10.1039/ c4an00068d

*Nanotechnology and the Environment*

10.1016/j.snb.2014.09.098

DOI: 10.1039/c4ra15872e

c8nj06208k

jelechem.2014.12.037

msec.2013.10.036

snb.2013.09.042

Wang M, Yang L. A novel

doped graphene modified electrode for determination of trace amounts of pesticide phoxim. Sensors and Actuators B: Chemical. 2015;**206**:495-501. DOI:

[168] Zheng Y, Liu Z, Jing Y, Li J, Zhan H. An acetylcholinesterase biosensor based on ionic liquid functionalized graphenegelatin-modified electrode for sensitive detection of pesticides. Sensors and Actuators B: Chemical. 2015;**210**:389- 397. DOI: 10.1016/j.snb.2015.01.003

[169] Zhang L, Zhang A, Du D, Lin Y. Biosensor based on Prussian blue nanocubes/reduced graphene oxide nanocomposite for detection of organophosphorus pesticides. Nanoscale. 2012;**4**:4674-4679. DOI:

[170] Zhao H, Ji X, Wang B, Wang N, Li X, Ni R, et al. An ultra-sensitive acetylcholinesterase biosensor based on reduced graphene oxide-Au

nanoparticles-β-cyclodextrin/Prussian

blue-chitosan nanocomposites for organophosphorus pesticides detection. Biosensors & Bioelectronics.

2015;**65**:23-30. DOI: 10.1016/j.

[171] Ensafi AA, Noroozi R, Zandi-Atashbar N, Rezaei B. Cerium (IV) oxide decorated on reduced graphene oxide, a selective and sensitive

[172] Shams N, Lim HN, Hajian R, Yusof NA, Abdullah J, Sulaiman Y, et al. A promising electrochemical sensor based on Au nanoparticles decorated reduced graphene oxide for selective detection of herbicide diuron in natural waters. Journal of Applied Electrochemistry. 2016;**46**:655-666. DOI: 10.1007/s10800-016-0950-4

[173] Yang Y, Asiri AM, Du D, Lin Y. Acetylcholinesterase biosensor based on a gold nanoparticle-

polypyrrole-reduced graphene oxide nanocomposite modified electrode for the amperometric detection of organophosphorus pesticides. Analyst.

electrochemical sensor for fenitrothion determination. Sensors actuators B Chem. 2017;**245**:980-987. DOI: 10.1016/j.

bios.2014.10.007

snb.2017.01.186

10.1039/c2nr30976a

[163] Zheng Y, Wang A, Lin H, Fu L, Cai W. A sensitive electrochemical sensor for direct phoxim detection based on an electrodeposited reduced graphene oxide-gold nanocomposite. RSC Advances. 2015;**5**:15425-15430.

[164] Karimian N, Fakhri H, Amidi S, Hajian A, Arduini F, Bagheri H. A novel sensing layer based on metal-organic framework UiO-66 modified with TiO2-graphene oxide: Application to rapid, sensitive and simultaneous determination of paraoxon and

chlorpyrifos. New Journal of Chemistry. 2019;**43**:2600-2609. DOI: 10.1039/

[165] Liu Q, Fei A, Huan J, Mao H, Wang K. Effective amperometric biosensor for carbaryl detection based on covalent immobilization acetylcholinesterase on multiwall carbon nanotubes/graphene oxide nanoribbons nanostructure. Journal of Electroanalytical Chemistry. 2015;**740**:8-13. DOI: 10.1016/j.

[166] Liu Y, Wang G, Li C, Zhou Q,

acetylcholinesterase biosensor based on carboxylic graphene coated with silver nanoparticles for pesticide detection. Materials Science and Engineering: C. 2014;**35**:253-258. DOI: 10.1016/j.

[167] Wang G, Tan X, Zhou Q, Liu Y, Wang M, Yang L. Synthesis of highly dispersed zinc oxide nanoparticles on carboxylic graphene for development a sensitive acetylcholinesterase biosensor. Sensors and Actuators B: Chemical. 2014;**190**:730-736. DOI: 10.1016/j.

**156**

[174] Li Y, Zhang Y, Han G, Xiao Y, Li M, Zhou W. An acetylcholinesterase biosensor based on graphene/ polyaniline composite film for detection of pesticides. Chinese Journal of Chemistry. 2016;**34**:82-88. DOI: 10.1002/cjoc.201500747

[175] Li Y, Shi L, Han G, Xiao Y, Zhou W. Electrochemical biosensing of carbaryl based on acetylcholinesterase immobilized onto electrochemically inducing porous graphene oxide network. Sensors and Actuators B: Chemical. 2017;**238**:945-953. DOI: 10.1016/j.snb.2016.07.152

[176] Bao J, Hou C, Chen M, Li J, Huo D, Yang M, et al. Plant esterasechitosan/gold nanoparticles-graphene nanosheet composite-based biosensor for the ultrasensitive detection of organophosphate pesticides. Journal of Agricultural and Food Chemistry. 2015;**63**:10319-10326. DOI: 10.1021/acs. jafc.5b03971

### *Edited by Mousumi Sen*

Nanotechnology is a vibrant area of research and a growing industry. The core scientific principles and applications of this interdisciplinary field bring together chemists, physicists, materials scientists, and engineers to meet the potential future challenges for sustainable development through new technologies and preparation of advanced materials with sustainable environmental protection. This book on Nanotechnology and the Environment includes the design and the sophisticated fabrication of nanomaterials along with their potential energy and environmental applications. This book is a significant contribution towards the development of the knowledge for all advanced undergraduate, graduate level students, researchers, and professional engineers leading in the fields of nanotechnology, nanochemistry, macromolecular science and those who have interest in energy and environmental science.

Published in London, UK © 2020 IntechOpen © ktsimage / iStock

Nanotechnology and the Environment

Nanotechnology

and the Environment

*Edited by Mousumi Sen*