Bulk and Nanocatalysts Applications in Advanced Oxidation Processes

*Luma Majeed Ahmed*

#### **Abstract**

Advanced oxidation processes (AOPs) are considered to be vital methods for treating the contaminations produced mainly by the human activations. In present-day, UV light or solar light, bulk and nano- photocatalysts are often used to enhance this technology by creating the highly reactive species such as the hydroxyl radicals. Extreme hydroxyl radical is considered as a key to start the photoreaction. Photoreaction is widely used in treatment of Lab and industrial contaminations, preparation of compounds and produced the renewable energy, so it's classified as green technique. In order to improve the efficiency of this reaction with fabrication the surface of the used photocatalyst such as metal doped, sensitized and produced a composite as bulk catalyst or nano catalyst.

**Keywords:** nanocatalysts, bulk catalyst, advanced oxidation processes, wastewater treatment, photocatalysis, Fenton reaction, photo-Fenton

#### **1. Introduction**

In this section, the advanced Oxidation Processes concepts will be related to use of the bulk and the nano- catalysts as vital materials for easily generating a highly oxidizing species and reactive oxygen species (ROSs) such as in aqueous or alcoholic solution [1]. ROSs are contains three primary kinds: superoxide anion (O2 •−), hydrogen peroxide (H2O2) and the hydroxyl radical (HO• ) [2], which produced from reaction of adsorbed oxygen molecule on catalyst's surface with one electron in conductive band under illumination by light as UV, or visible or solar light, this mechanism is useful to reduce the recombination process and increased the life time of hole in valance band [3, 4]. As explained in **Figure 1**.

The ROSs are having the electron configurations as tabled in **Table 1** [5–8].

#### **2. Advance oxidation process applications**

In the last few years, several researches have predominated in many universities and research centers on the scientific ventures to mainly treat the contaminations that produced by textile factories [9–11], reduced the degradation of food's

**Figure 1.**

*Essential mechanism for generating the ROSs under illumination of photo-catalyst particles [1].*


#### **Table 1.**

*Electronic configurations and chemical formulas for the ROSs types.*

dye [12], decolorization of colored organometallic complexes [13], degradation of toxic cyclic compounds [14] and produced a hydrogen from alcohol as renewable energy [15]. The effective materials for all above mention research are generated the hydroxyl radical in aqueous solution with maximum oxidation power equals to 2.8 V [1]. Based on to the AOPs, the common sources for creation

**109**

of.

**Figure 2.**

or photo reactions [1, 16–19].

*Schematic diagram of common sources of.*

4.Have low economic cost.

**3. Bulk and nano-catalysts**

mentioned in **Figure 3** [22–24].

treat their problems.

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes*

OH in AOPs are illustrated in **Figure 2**, which regards as power to star the dark

*OH in advanced oxidation processes.*

2.Have the appropriate potential to depress the hazardous organic pollutants by

Whereas, the drawbacks of AOPs [1, 21] are quenching the reaction rate with increasing the scavenger contains (mostly peroxide ion) and may be generated the undesirable hazardous products that prevented the complete of mineralization process, hence, the altered of pH or using further cost steps may be essentially to

In general, the catalysts may be metal or alloy or semiconductor. Semiconductor is wide used as catalyst and can be element or compound as amorphous or crystalline or rock salt crystal. Because of semiconductors have intermediate properties between metal and insulator, which has given them rescannable electronic and structural properties, hence, semiconductor is classified as a better-known kinds, as

The usages of the bulk and nano catalysts are increment with increasing the development of life activations. The catalysts were known for the long time to increase the rate of reaction with decreasing the time of reaction and the activation energy in dark reaction or photoreaction. In order to use the catalyst in

Fortunately, the benefits of AOPs are more than those of drawbacks. The

complete their mineralization and producing CO2 and H2O.

benefits of AOPs are summarized up as [1, 20] follows to:

1.Create a large number of free radicals species.

3.Reduce the time of dark or photoreaction.

*DOI: http://dx.doi.org/10.5772/intechopen.94234*

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes DOI: http://dx.doi.org/10.5772/intechopen.94234*

#### **Figure 2.**

*Oxidoreductase*

**Figure 1.**

**108**

**Table 1.**

dye [12], decolorization of colored organometallic complexes [13], degradation of toxic cyclic compounds [14] and produced a hydrogen from alcohol as renewable energy [15]. The effective materials for all above mention research are generated the hydroxyl radical in aqueous solution with maximum oxidation power equals to 2.8 V [1]. Based on to the AOPs, the common sources for creation

*Electronic configurations and chemical formulas for the ROSs types.*

*Essential mechanism for generating the ROSs under illumination of photo-catalyst particles [1].*

*Schematic diagram of common sources of. OH in advanced oxidation processes.*

of. OH in AOPs are illustrated in **Figure 2**, which regards as power to star the dark or photo reactions [1, 16–19].

Fortunately, the benefits of AOPs are more than those of drawbacks. The benefits of AOPs are summarized up as [1, 20] follows to:


Whereas, the drawbacks of AOPs [1, 21] are quenching the reaction rate with increasing the scavenger contains (mostly peroxide ion) and may be generated the undesirable hazardous products that prevented the complete of mineralization process, hence, the altered of pH or using further cost steps may be essentially to treat their problems.

#### **3. Bulk and nano-catalysts**

In general, the catalysts may be metal or alloy or semiconductor. Semiconductor is wide used as catalyst and can be element or compound as amorphous or crystalline or rock salt crystal. Because of semiconductors have intermediate properties between metal and insulator, which has given them rescannable electronic and structural properties, hence, semiconductor is classified as a better-known kinds, as mentioned in **Figure 3** [22–24].

The usages of the bulk and nano catalysts are increment with increasing the development of life activations. The catalysts were known for the long time to increase the rate of reaction with decreasing the time of reaction and the activation energy in dark reaction or photoreaction. In order to use the catalyst in

#### **Figure 3.** *Better-known kinds of semiconductors.*

**Figure 4.** *Band gap energy positions of different photo-semiconductor at pH = 1.*

photoreaction as photo catalyst, must have a band gap with raged about 1.1 eV to 5.0 eV [1, 24]. Referring to **Figure 4**, several band gap energy positions of some common photo catalysts can be displayed [1, 25–27].

The mainly problem in bulk and nano catalyst is recombination process, which results in diminishing the efficiency of used photocatalyst by returning the photoelectron from conductive band to valance band and reacting with photohole immediately. The recombination includes four kinds can be followed in **Table 2** and **Figure 5** [1, 28–30].

In order to improve the activity of photocatalysts must depress the recombination with modify their surfaces with three main methods: surface sensitization, metalized photocatalyst surface and coupled for two or more photocatalysts as Composite. The details of these modification methods are mention in **Table 3** and **Figure 6** [40].

**111**

**Figure 5.**

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes*

Band-to- band recombination

Centers recombination or Trap-assisted recombination

Recombination of an exciton

**Kinds Other name Info Type of** 

In this kind, the transition occurrs as a radiative transition in direct band gap semiconductor. It is created when the Free photo electron in CB drops directly into free photo hole (an unoccupied state) in the VB and associated together. Note **Figure 5(A)**.

This case obtains, when defect of semiconductor by impurities that given a new levels (as traps of photoelectron and photohole). It leads to liberate heat as phonon in indirect band gap semiconductor. Note **Figure 5(B)**.

This case occurs at low temperature, when the traps at or near the surface or interface of the semiconductor, capture the photo electron- hole as exciton. That attitude to dangling bonds caused by the sudden discontinuation of the semi-conductor crystal with energy just below the band gap value. Note

carriers: Free photo electron, free photo whole recombine, and the emitting the energy as heat or as a photon (non-radiative process). The transition of energy deals with as intra-band transitions, which resulting when either electron elevates in higher levels of conduction band or hole deeper push into the valence band. Note

**Figure 5(C)**.

— This recombination involves three

**Figure 5(D)**.

**photocatalyst**

Pure TiO2 and defect of TiO2 by metal, which had given an indirect band gap.

It happed in solar cells and light emitting diode (LED) containing shallow levels.

This case can be obtained wit short lifetime when heavy doping defects (like Ag) in direct-gap semiconductors under present sunlight.

ZnO have a direct band gap.

*DOI: http://dx.doi.org/10.5772/intechopen.94234*

Direct recombination

Volume recombination

Surface recombination

Auger recombination

**Table 2.**

*The most common recombination types concepts.*

*The schematic diagram of the most common recombination kinds.*


#### *Bulk and Nanocatalysts Applications in Advanced Oxidation Processes DOI: http://dx.doi.org/10.5772/intechopen.94234*

#### **Table 2.**

*Oxidoreductase*

**110**

**Figure 4.**

**Figure 3.**

*Better-known kinds of semiconductors.*

and **Figure 5** [1, 28–30].

and **Figure 6** [40].

photoreaction as photo catalyst, must have a band gap with raged about 1.1 eV to 5.0 eV [1, 24]. Referring to **Figure 4**, several band gap energy positions of some

The mainly problem in bulk and nano catalyst is recombination process, which results in diminishing the efficiency of used photocatalyst by returning the photoelectron from conductive band to valance band and reacting with photohole immediately. The recombination includes four kinds can be followed in **Table 2**

In order to improve the activity of photocatalysts must depress the recombination with modify their surfaces with three main methods: surface sensitization, metalized photocatalyst surface and coupled for two or more photocatalysts as Composite. The details of these modification methods are mention in **Table 3**

common photo catalysts can be displayed [1, 25–27].

*Band gap energy positions of different photo-semiconductor at pH = 1.*

*The most common recombination types concepts.*


**113**

**Figure 6.**

Textile dye Reactive red 2 dye

Textile dye direct orange dye

Textile dye reactive yellow 14

Industrial dye Chlorazol black BH dye

Industrial dye Acid Red 87(Eosin (Eosin Yellow) dye

Textile dye Dispersive yellow

42 dye

dye

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes*

*DOI: http://dx.doi.org/10.5772/intechopen.94234*

*Schematic diagram for modification of photocatalyst surface [40].*

H2O2

O2/UV-A(250 W)/ZnO/

O2/UV-A(125 W)/ZnO

O2/UV-A(250 W)/ZnO

O2/UV-A(125 W)/ZnO

O2/UV-A(125 W)/ZnO/Fe2+

O2/UV-A(125 W)/ZnO/ Fe2++1% H2O2

O2/Solar/ZnO

O2/UV-A(250 W)/ZnO 92.7%

O2/UV-A(250 W)/ZnO 91.41%

O2/UV-A/ZnO 99.07%

**Application field Type of used AOPs Efficiency References**

89.8% (Photodecolorization) (5 mmole/L) of H2O2 (T = 25°C), (pH = 10)

(Photodecolorization) (T = 35°C), (pH = 6.68)

(Photodecolorization) (T = 38°C), (pH = 6.75)

(Photodecolorization) (T = 15°C), (pH = 7.63)

(Photodecolorization) (T = 38°C), (pH = 8.6)

(Photodecolorization) (T = 38°C), (pH = 8.6)

(Photodecolorization) (T = 42°C), (pH = 8.6)

(Photodecolorization) (T = 20°C), (pH = 7.7) 60.86% (Photodecolorization) (T = 20°C), (pH = 7.7) 16.44% (Photodecolorization) (5 x 10−4 mole/L) of Fe2+ (T = 20°C), (pH = 7.7)

74.4.5%

98.5%

96.5%

94.40%

[41]

[42]

[43]

[44]

[32]

[10]

**Table 3.** *The description of the methods for modifying photocatalysts [31–39].*

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes DOI: http://dx.doi.org/10.5772/intechopen.94234*

#### **Figure 6.**

*Oxidoreductase*

**112**

**Table 3.**

*The description of the methods for modifying photocatalysts [31–39].*

*Schematic diagram for modification of photocatalyst surface [40].*



**115**

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes*

O2/UV-A(125 W)/ TiO2 NPS

O2/UV-A(125 W)/ TiO2

O2/UV-A(125 W)/ TiO2

O2/UV-A(125 W)/ TiO2 NPS/ 0.1% H2O2

O2/UV-A(125 W)/ TiO2 NPS/ 0.1% H2O2+ Fe2+

O2/UV-A(250 W)/ TiO2 NPS

O2/UV-A(250 W)/ TiO2

O2/UV-A(250 W)/ WO3

O2/UV-A(250 W)/ WO3

O2/UV-A(250 W)/ (0.5) WO3-TiO2 nanocomposite O2/UV-A(250 W)/ (0.5) WO3-TiO2 nanocomposite+

O2/UV-A(250 W)/ZrO2

O2/UV-A(250 W)/ ZrO2 + Fe2+

O2/UV-A(250 W)/ ZrO2 + 1.5% H2O2

O2/UV-A(250 W)/ ZrO2 + K2S2O8

O2/UV-A(400 W)/ (1)Mn3O4- (4) ZrO2 nanocomposite

O2/UV-A(400 W)/ Mn3O4

NPS+ H2O2

NPS+ H2O2

NPS

H2O2

NPS/ Fe2+

NPS/ Fe2+

**Application field Type of used AOPs Efficiency References**

90.2%

85.92%

92.73%

98.83%

63.58%

50.44%

27.84%

21.54%

25.11%

73.88%

92.31%

39.93%

98.78%

74.62%

22.64%

40%

(Photodecolorization) (T = 30°C), (pH = 6)

[34]

[16]

[46]

[47]

(Photodecolorization) (1 x 10−4 mole/L) of Fe2+ (T = 30°C), (pH = 6)

(Photodecolorization) (T = 30°C), (pH = 6)

(Photodecolorization) (1 x 10−4 mole/L) of Fe2+ (T = 30°C), (pH = 6)

(Photodecolorization) (T = 25°C), (pH = 6.09)

(Photodecolorization) (1 x 10−2 mmole/L) of H2O2 (T = 25°C), (pH = 6.09)

(Photodecolorization) (T = 25°C), (pH = 6.09)

(Photodecolorization) (1 x 10−2 mmole/L) of H2O2 (T = 25°C), (pH = 6.09)

(Photodecolorization) (T = 25°C), (pH = 6.09)

(Photodecolorization) (1 x 10−2 mmole/L) of H2O2 (T = 25°C), (pH = 6.09)

(Photodecolorization) (T = 30°C), (pH = 5.4)

(Photodecolorization) (1 x 10−4 mmole/L) of Fe2+ (T = 30°C), (pH = 5.4)

(Photodecolorization) (T = 30°C), (pH = 5.4)

(Photodecolorization) (1 x 10−4 mmole/L) of K2S2O8 (T = 30°C), (pH = 5.4)

(Photodecolorization) (T = 15°C), (pH = 4)

(Photodecolorization) (T = 17°C), (pH = 4)

*DOI: http://dx.doi.org/10.5772/intechopen.94234*

Industrial dye Safranine O Dye

Industrial dye Acid Red 87 (Eosin Yellow) dye

Industrial dye Methyl green dye

Lab materials Fe(II)-(4,5- DIAZAFLUOREN-9- ONE 11) COMPLEX


*Oxidoreductase*

Drug dye Cobalamine(Vit

Food dye Carmoisine (E122)

Lab materials Co(II) Complex of Schiff Base

Industrial dye Methyl green dye

Liberated of hydrogen from Methanol as renewable energy

Industrial dye Light Green SF Yellowish (Acid Green 5) Dye

dye

B12)

**Application field Type of used AOPs Efficiency References**

79.33%

88.75%

90.80%

95.85%

73.11%

62.58%

36.99%

37%

87.37%

8.8%

4.5%

90.2%

88.1%

(Photodecolorization) (T = 30°C), (pH = 6.5) [19]

[12]

[13]

[35]

[14]

[45]

(Photodecolorization) (1 x 10−4 mole/L) of K2S2O8 (T = 30°C), (pH = 6.5)

(Photodecolorization) (T = 30°C), (pH = 6.5)

(Photodecolorization) (1 x 10−4 mole/L) of K2S2O8 (T = 30°C), (pH = 6.5)

(Photodecolorization) (T = 18°C), (pH = 7.55)

(Photodecolorization) (T = 18°C), (pH = 7.55)

(Photodecolorization) (1 x 10−5 mole/L) of Fe2+ (T = 18°C), (pH = 7.55)

(Photodecolorization) (T = 38°C), (pH = 7.55)

(Photodecolorization) (T = 25°C), (pH = 5.4)

(Photodecolorization) (T = 25°C), (pH = 5.4)

(Photo hydrogen production) (T = 25°C), (pH = 7.3)

(Photo hydrogen production) (T = 25°C), (pH = 7.3)

(Photodecolorization) (T = 20°C), (pH = 7.3)

(Photodecolorization) (T = 20°C), (pH = 7.3)

O2/UV-A(250 W)/ZnO

O2/UV-A(250 W)/ZnO/

O2/UV-A(250 W)/ZnO/

O2/UV-A(250 W)/ZnO/ K2S2O8 + 0.025% H2O2

O2/UV-A(250 W)/ZnO

O2/UV-A(250 W)/ZnO/

O2/UV-A(400 W)/ ZnO

O2/UV-A(400 W)/Ag(2%)

Ar/UV-B(1000 W)/ (0.5 Pt)

Ar/UV-B(1000 W)/ (0.5

O2/UV-A(400 W)/ TiO2

O2/UV-A(400 W)/ TiO2

NPS

ZnO NPs

TiO2 NPS

NPS

Au) TiO2 NPS

O2/UV-A(250 W)/ZnO/ Fe2+

O2/UV-A(250 W)/ZnO 99.11%

0.1% H2O2

K2S2O8

0.025% H2O2

**114**


**Table 4.**

*Some applications of bulk and nano photocatalydts in AOPs, with environment chemistry and green chemistry.*

#### **4. Used of bulk or nano catalyst in AOPs**

There are many common application of AOPs in environment fields by using the white photocatalyst or its modified such as ZnO, TiO2 ZrO2, ZnS, WO3, CdS and Mn3O4. The efficiencies with used these photocatalysts are altered with using AOPs methods. The efficiency of the photoreaction depends mostly on the concentration of colored material, initial pH which affected on the surface of photocatalyst and the temperature. As shown in **Table 4**.

#### **5. Conclusions**

This chapter focuses on the source of hydroxyl radical which produces via the advance oxidation process. Indeed, this process interests in the forming the different species, which in the final step generates a hydroxyl radical. The photocatalyst enhances the generating of hydroxyl radicals (2.8 V) in aqueous solution under Uv- light or visible or solar. The photoexitation of photocatalyst leads to jump of electon to conductive band then return to valance band and liberates a hot this process called recombination. It is depressed the efficiency of photoreaction. However, some procedures used to modify the photocatalyst surface.

#### **Acknowledgements**

The author wants to thank his family for helping him in carrying out this work.

**117**

**Author details**

Luma Majeed Ahmed

Department of Chemistry, College of Science, University of Kerbala, Kerbala, Iraq

© 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: luma.ahmed@uokerbala.edu.iq

provided the original work is properly cited.

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes*

*DOI: http://dx.doi.org/10.5772/intechopen.94234*

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes DOI: http://dx.doi.org/10.5772/intechopen.94234*

*Oxidoreductase*

Textile dye Reactive blue 5 dye

Industrial dye Congo red dye

**Table 4.**

**4. Used of bulk or nano catalyst in AOPs**

NPs

the temperature. As shown in **Table 4**.

modify the photocatalyst surface.

**Acknowledgements**

**5. Conclusions**

There are many common application of AOPs in environment fields by using the white photocatalyst or its modified such as ZnO, TiO2 ZrO2, ZnS, WO3, CdS and Mn3O4. The efficiencies with used these photocatalysts are altered with using AOPs methods. The efficiency of the photoreaction depends mostly on the concentration of colored material, initial pH which affected on the surface of photocatalyst and

*Some applications of bulk and nano photocatalydts in AOPs, with environment chemistry and green chemistry.*

**Application field Type of used AOPs Efficiency References**

59%

94%

95%

98%

(Photodecolorization) (T = 15°C), (pH = 6.3)

[36]

[39]

(Photodecolorization) (T = 17°C), (pH = 4.1)

(Photodecolorization) (T = 30°C), (pH = 7.5)

(Photodecolorization) (T = 30°C), (pH = 7.5)

O2/UV-A(400 W)/ ZnS NPs

O2/UV-A(400 W)/ Cr-ZnS

O2/UV-A(400 W)/ ZnS NPs

O2/UV-A(400 W)/ CdS-ZnS

nanocomposite

This chapter focuses on the source of hydroxyl radical which produces via the advance oxidation process. Indeed, this process interests in the forming the different species, which in the final step generates a hydroxyl radical. The photocatalyst enhances the generating of hydroxyl radicals (2.8 V) in aqueous solution under Uv- light or visible or solar. The photoexitation of photocatalyst leads to jump of electon to conductive band then return to valance band and liberates a hot this process called recombination. It is depressed the efficiency of photoreaction. However, some procedures used to

The author wants to thank his family for helping him in carrying out this work.

**116**

#### **Author details**

Luma Majeed Ahmed Department of Chemistry, College of Science, University of Kerbala, Kerbala, Iraq

\*Address all correspondence to: luma.ahmed@uokerbala.edu.iq

© 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.

### **References**

[1] Ahmed L, and Hussein F. Roles of Photocatalytic Reactions of Platinized TiO2 Nanoparticales. 1st ed. LAP Lambert Academia Published; 2014. 103 P. ISBN-10: 3659538817.

[2] Collin F. Chemical Basis of Reactive Oxygen Species Reactivity and Involvement in Neurodegenerative Diseases. Int. J. Mol. Sci. 2019; 20, 2407:1-17. DOI: 10.3390/ijms20102407.

[3] Ahmed L, Ivanova I, Hussein F and Bahnemann D. Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions. International Journal of Photoenergy. 2014; 1:1-9. DOI: 10.1155/2014/503516.

[4] Ahmed L, Hussen F, Mahdi A. Photocatalytic Dehydrogenation of Aqueous Methanol Solution by Naked and Platinized TiO2 Nanoparticles. Asian Journal of Chemistry. 2012; 24(12): 5564-5568. DOI:

[5] Krumova K, Cosa G. Chapter 1:Overview of Reactive Oxygen Species . In: Nonell S, Flors *C,* editors. Singlet Oxygen: Applications in Biosciences and Nanosciences, Volume 1. Uk: Royal social of chemistry; 2016, p. 1-21 DOI: 10.1039/9781782622208-00001

[6] Halliwell B, Gutteridge J. *Free Radicals in Biology and Medicine* , 5th ed. Oxford Oxford: University Press; 2007. 961 P. ISBN 978-0-19-871747-8 (hbk.). ISBN 978-0-19-871748-5 (pbk.)

[7] Sharma S, Ruparelia J, Patel M. A general review on Advanced Oxidation Processes for waste water treatment. Institute of Technology. Nirma University. Ahmed Abad. 2011: 382-481.

[8] Bielski B, Cabelli D, Arudi R, Ross A. Reactivity of HO2/O2 Radicals in Aqueous Solution. J. Phys. Chem. Ref. Data. 1985; 14(4):1041-1100.

[9] Karam F, Saeed N, Al-Yasari A, Ahmed L, Saleh H. Kinetic Study for Reduced the Toxicity of Textile Dyes (Reactive Yellow 14 Dye and Reactive Green Dye) Using UV-A Light/ ZnO System. Egypt. J. Chem. 2020; 63(8): 211-224. DOI: 10.21608/ ejchem.2020.25893.2511.

[10] Alattar R, Saleh H , AL-Hilfi J, Ahmed L. Influence the addition of Fe2+ and H2O2 on removal and decolorization of textile dye (dispersive yellow 42 dye). Egypt. J. Chem., 2020; 63(9): 3191-3201. DOI:10.21608/ EJCHEM.2020.23542.2400.

[11] Kzar K, Mohammed Z, Saeed S, Ahmed L, Kareem D, Hadyi H, Kadhim A. Heterogeneous photodecolourization of cobaltous phthalocyaninate dye (reactive green dye) catalyzed by ZnO. In AIP Conference Proceedings, 2144(1)020004, AIP Publishing LLC,2019: 020004-01 -020004-10 .

[12] Ahmed L, Jassim M, Mohammed M and Hamza D. Advanced oxidation processes for carmoisine (E122) dye in UVA/ZnO system: Influencing pH, temperature and oxidant agents on dye solution. Journal of Global Pharma Technology. 2018; 10(07): 248-254.

[13] Abass S, Al-Hilfi J, Abbas S and Ahmed L. Preparation, Characterization and Study the Photodecolorization of Mixed-Ligand Binuclear Co(II) Complex of Schiff Base by ZnO. Indonesian Journal of Chemistry. 2020; 20(2):404-412.

[14] Ahmed L, Al-Kaim A, Halbus A, Hussein F. Photocatalytic hydrogen production from aqueous methanol solution over metallized TiO2. International Journal of ChemTech. 2016; 9(10):90-98.

**119**

CH 1.

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes*

[23] Yacobi B. Semiconductor Materials-An Introduction to Basic Principles. 1st ed. New York : Kluwer Academic

[24] Singh V. Band Gap and Resistivity Measurements of Semiconductor Materials For Thin Films. Journal of Emerging Technologies and Innovative

[25] Material S. Physics Semiconductors and Band Theory, 1st ed. HIGHER: Learning and Teaching Scotland;2011.

[26] Carp O, Huisman C and Reller A. Photoinduced reactivity of titanium dioxide, Prog. Solid State Chem. 2004;

Heterogeneous photocatalyst materials for water splitting. Chem Soc Rev.2009;

[29] Pierret R. Advanced semiconductor Fundemantals. 1st ed. vol. VI, Modular series on solid state devices, New Jersey : Pearson Education, Inc. Upper Saddle

[28] Kuang W, Tolner H, and Li Q. Cathode-luminescence diagnostics of MgO, MgO:Si, MgO:Sc, and MgCaO . Journal of the SID . 2012; 20(1): 63- 69S.

[27] Kudo A. and Miseki Y.

River;2002. 07458 p. CH5.

[30] Hayawi M. Preparation,

Kerbala University:2020.

Characterization of Spinel Mn3O4/ ZrO2 Composite and Application on Colored Material[MSC thesis]. Karbala:

[31] Giwa A, Nkeonye P., Bello K., Kolawole G. and Campos A. Solar Photocatalytic Degradation of

Reactive Yellow 81 and Reactive Violet 1 in Aqueous Solution Containing Semiconductor Oxides. International Journal of Applied Science and Technology. 2012; 2(4): 90-105.

Research (JETIR). 2017; 4(12):

Publishers. 2004. CH 6.

1200-1210.

4-5 pp.

32: 33-177.

38: 253-278.

*DOI: http://dx.doi.org/10.5772/intechopen.94234*

[15] Karam, F, Hussein, F, Baqir S, Halbus A, Dillert R, Bahnemann, D. Photocatalytic degradation of anthracene in closed system reactor. International Journal of Photoenergy.

[16] Jawad T, Ahmed L. Direct Ultrasonic Synthesis of WO3/TiO2 Nanocomposites and applying them in the Photodecolorization of Eosin Yellow Dye. Periódico Tchê Química. 2020;

[17] Stasinakis A. Use of Selected Advanced Oxidation Processes (AOPs) For Wastewater Treatment –A mini review. Global NEST Journal. 2008;

[18] Marhoon A, Saeed S, Ahmed L. Application of some effects on the Degradation of the aqueous solution of Fuchsine dye by photolysis. Journal of Global Pharma Technology. 2019; 11(9):

[19] Ahmed L, Saaed S, Marhoon A. Effect of Oxidation Agents on Photo-Decolorization of Vitamin B12 in the Presence of ZnO/UV-A System. Indones.

Fukushi K. Hybrid Treatment Systems

Reviews .Environmental Science and Technology. 2007; 37(4): 315-377.

[22] Yu P, and Cardona M. Fundamentals

Materials Properties. 4th ed. Germany : Springer-Verlag Berlin Heidelberg; 2010.

of Semiconductors Physics and

J. Chem. 2018; 18: 272-278.

[20] Hai F, Yamamoto K,

for Dye Wastewater. Critical

[21] Robinson T, McMullan G, Marchant R, Nigam P. Remediation of dyes in textile effluent: a critical review on current treatment technologies with a proposed alternative. Bioresource Technology.

2001; 77: 247-255.

2014; 1: 1-6.

17(34): 621-633.

10(3): 376-385.

76-81.

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes DOI: http://dx.doi.org/10.5772/intechopen.94234*

[15] Karam, F, Hussein, F, Baqir S, Halbus A, Dillert R, Bahnemann, D. Photocatalytic degradation of anthracene in closed system reactor. International Journal of Photoenergy. 2014; 1: 1-6.

[16] Jawad T, Ahmed L. Direct Ultrasonic Synthesis of WO3/TiO2 Nanocomposites and applying them in the Photodecolorization of Eosin Yellow Dye. Periódico Tchê Química. 2020; 17(34): 621-633.

[17] Stasinakis A. Use of Selected Advanced Oxidation Processes (AOPs) For Wastewater Treatment –A mini review. Global NEST Journal. 2008; 10(3): 376-385.

[18] Marhoon A, Saeed S, Ahmed L. Application of some effects on the Degradation of the aqueous solution of Fuchsine dye by photolysis. Journal of Global Pharma Technology. 2019; 11(9): 76-81.

[19] Ahmed L, Saaed S, Marhoon A. Effect of Oxidation Agents on Photo-Decolorization of Vitamin B12 in the Presence of ZnO/UV-A System. Indones. J. Chem. 2018; 18: 272-278.

[20] Hai F, Yamamoto K, Fukushi K. Hybrid Treatment Systems for Dye Wastewater. Critical Reviews .Environmental Science and Technology. 2007; 37(4): 315-377.

[21] Robinson T, McMullan G, Marchant R, Nigam P. Remediation of dyes in textile effluent: a critical review on current treatment technologies with a proposed alternative. Bioresource Technology. 2001; 77: 247-255.

[22] Yu P, and Cardona M. Fundamentals of Semiconductors Physics and Materials Properties. 4th ed. Germany : Springer-Verlag Berlin Heidelberg; 2010. CH 1.

[23] Yacobi B. Semiconductor Materials-An Introduction to Basic Principles. 1st ed. New York : Kluwer Academic Publishers. 2004. CH 6.

[24] Singh V. Band Gap and Resistivity Measurements of Semiconductor Materials For Thin Films. Journal of Emerging Technologies and Innovative Research (JETIR). 2017; 4(12): 1200-1210.

[25] Material S. Physics Semiconductors and Band Theory, 1st ed. HIGHER: Learning and Teaching Scotland;2011. 4-5 pp.

[26] Carp O, Huisman C and Reller A. Photoinduced reactivity of titanium dioxide, Prog. Solid State Chem. 2004; 32: 33-177.

[27] Kudo A. and Miseki Y. Heterogeneous photocatalyst materials for water splitting. Chem Soc Rev.2009; 38: 253-278.

[28] Kuang W, Tolner H, and Li Q. Cathode-luminescence diagnostics of MgO, MgO:Si, MgO:Sc, and MgCaO . Journal of the SID . 2012; 20(1): 63- 69S.

[29] Pierret R. Advanced semiconductor Fundemantals. 1st ed. vol. VI, Modular series on solid state devices, New Jersey : Pearson Education, Inc. Upper Saddle River;2002. 07458 p. CH5.

[30] Hayawi M. Preparation, Characterization of Spinel Mn3O4/ ZrO2 Composite and Application on Colored Material[MSC thesis]. Karbala: Kerbala University:2020.

[31] Giwa A, Nkeonye P., Bello K., Kolawole G. and Campos A. Solar Photocatalytic Degradation of Reactive Yellow 81 and Reactive Violet 1 in Aqueous Solution Containing Semiconductor Oxides. International Journal of Applied Science and Technology. 2012; 2(4): 90-105.

**118**

*Oxidoreductase*

**References**

P. ISBN-10: 3659538817.

[1] Ahmed L, and Hussein F. Roles of Photocatalytic Reactions of Platinized TiO2 Nanoparticales. 1st ed. LAP Lambert Academia Published; 2014. 103 [9] Karam F, Saeed N, Al-Yasari A, Ahmed L, Saleh H. Kinetic Study for Reduced the Toxicity of Textile Dyes (Reactive Yellow 14 Dye and Reactive Green Dye) Using UV-A Light/ ZnO System. Egypt. J. Chem. 2020; 63(8): 211-224. DOI: 10.21608/ ejchem.2020.25893.2511.

[10] Alattar R, Saleh H , AL-Hilfi J, Ahmed L. Influence the addition of Fe2+ and H2O2 on removal and decolorization

of textile dye (dispersive yellow 42 dye). Egypt. J. Chem., 2020; 63(9): 3191-3201. DOI:10.21608/ EJCHEM.2020.23542.2400.

[11] Kzar K, Mohammed Z,

2144(1)020004, AIP


20(2):404-412.

2016; 9(10):90-98.

Publishing LLC,2019: 020004-01

[12] Ahmed L, Jassim M, Mohammed M and Hamza D. Advanced oxidation processes for carmoisine (E122) dye in UVA/ZnO system: Influencing pH, temperature and oxidant agents on dye solution. Journal of Global Pharma Technology. 2018; 10(07): 248-254.

[13] Abass S, Al-Hilfi J, Abbas S and Ahmed L. Preparation, Characterization and Study the Photodecolorization of Mixed-Ligand Binuclear Co(II) Complex of Schiff Base by ZnO. Indonesian Journal of Chemistry. 2020;

[14] Ahmed L, Al-Kaim A, Halbus A, Hussein F. Photocatalytic hydrogen production from aqueous methanol solution over metallized TiO2. International Journal of ChemTech.

Saeed S, Ahmed L, Kareem D, Hadyi H, Kadhim A. Heterogeneous photodecolourization of cobaltous phthalocyaninate dye (reactive green dye) catalyzed by ZnO. In AIP Conference Proceedings,

[2] Collin F. Chemical Basis of Reactive

Oxygen Species Reactivity and Involvement in Neurodegenerative Diseases. Int. J. Mol. Sci. 2019; 20, 2407:1-17. DOI: 10.3390/ijms20102407.

[3] Ahmed L, Ivanova I, Hussein F and Bahnemann D. Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions. International Journal of Photoenergy. 2014; 1:1-9. DOI: 10.1155/2014/503516.

[4] Ahmed L, Hussen F, Mahdi A. Photocatalytic Dehydrogenation of Aqueous Methanol Solution by Naked and Platinized TiO2 Nanoparticles. Asian Journal of Chemistry. 2012;

[5] Krumova K, Cosa G. Chapter 1:Overview of Reactive Oxygen Species . In: Nonell S, Flors *C,* editors. Singlet Oxygen: Applications in Biosciences and Nanosciences, Volume 1. Uk: Royal social of chemistry; 2016, p. 1-21 DOI:

10.1039/9781782622208-00001

[6] Halliwell B, Gutteridge J. *Free* 

*Radicals in Biology and Medicine* , 5th ed. Oxford Oxford: University Press; 2007. 961 P. ISBN 978-0-19-871747-8 (hbk.). ISBN 978-0-19-871748-5 (pbk.)

[7] Sharma S, Ruparelia J, Patel M. A general review on Advanced Oxidation Processes for waste water treatment. Institute of Technology. Nirma

University. Ahmed Abad. 2011: 382-481.

[8] Bielski B, Cabelli D, Arudi R, Ross A. Reactivity of HO2/O2 Radicals in Aqueous Solution. J. Phys. Chem. Ref.

Data. 1985; 14(4):1041-1100.

24(12): 5564-5568. DOI:

[32] Ahmed L. Photo-decolorization kinetics of acid red 87 dye in ZnO suspension under different types of UV-A light. Asian J. Chem. 2018; 30(9): 2134-2140.

[33] Pare B, Singh P and Jonnalagadda S, Visible Light-drive Photocatalytic Degradation and Minieralization of neutral Red dye in a sulurry Photoreactor. Indian Journal Chemistry Technoogy.2010; 17: 391-395.

[34] Jasim K, and Ahmed L. TiO2 Nanoparticles Sensitized by Safranine O Dye using UV-A Light System. In IOP Conference Series. Materials Science and Engineering. 2019; 571(012064):1-9.

[35] Fadhil F, Ahmed L, and Mohammed A. Effect of silver doping on structural and photocatalytic circumstances of ZnO nanoparticles. Iraqi Journal of Nanotechnolog, Synthesis and Application. 2020; 1: 13-20.

[36] Mahammed B, and Ahmed L. Enhanced Photocatalytic Properties of Pure and Cr-Modified ZnS Powders Synthesized by Precipitation Method. Journal of Geoscience and Environment Protection. 2017; 5: 101-111.

[37] Mohammed B, and Ahmed L. Improvement the Photo Catalytic Properties of ZnS nanoparticle with Loaded Manganese and Chromium by Co-Precipitation Method. Journal of Global Pharma Technology. 2018; 10(7):129-138.

[38] Jawad T. Synthesis and Characterization of Nano-Composite WO3/ TiO2 by Using Ultrasonic and it is Application on Photodecolorization of Eosin Yellow Dye [ MSC thesis]. Karbala: Kerbala University: 2020.

[39] Fakhri F, and Ahmed L. Incorporation CdS with ZnS as nanocomposite and Using in Photo-Decolorization of Congo Red Dye. Indones. J. Chem.2019; 19(4):936-943.

[40] Fakhri F. Preparation, Characterization of ZnS/CdS Composites nano particles and using in photocatalytic-decolorization of Congo red dye[ MSC thesis]. Karbala: Kerbala University: 2019.

[41] Mashkour M, Al-Kaim A, Ahmed L, and Hussein F. Zinc Oxide Assisted Photocatalytic Decolourization of Reactive Red 2 Dye. Int. J. Chem. Sci. 2011; 9(3): 969-979.

[42] Zuafuani S, and Ahmed L. Photocatalytic Decolourization of Direct Orange Dye by Zinc Oxide under UV Irradiation. Int. J. Chem. Sci.2015; 13(1):187-196.

[43] Ahmed L, Tawfeeq F, Abed Al-Ameer F, Abed Al-Hussein K. and Athaab A. Photo-Degradation of Reactive Yellow 14 Dye (A Textile Dye) Employing ZnO as Photocatalyst. Journal of Geoscience and Environment Protection.2016; 4: 34-44.

[44] Abbas S, Hassan Z, and Ahmed L. Influencing the Artificial UV-A light on decolorization of Chlorazol black BH Dye via using bulk ZnO Suspensions. In Journal of Physics: Conference Series. IOP Publishing. 052050. 2019; 1294(5):1-8.

[45] Eesa M, Juda A, and Ahmed L. Kinetic and thermodynamic study of the photocatalytic decolourization of light green SF yellowish (acid green 5) dye using commercial bulk Titania and commercial Nanotitania. Int. J. Sci. Res.2016; 5(11): 1495-1500.

[46] Hussein Z, Abbas S, and Ahmed, L. UV-A activated ZrO2 via photodecolorization of methyl green dye. In IOP Conference Series: Materials

**121**

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes*

*DOI: http://dx.doi.org/10.5772/intechopen.94234*

Science and Engineering. 012132, IOP

Publishing. 2018; 454(1): 1-11.

[47] Hayawi M, Kareem M, and Ahmed L. Synthesis of Spinel Mn3O4 and Spinel Mn3O4/ZrO2 Nanocomposites and Using Them in Photo-Catalytic Decolorization of Fe(II)-(4,5-Diazafluoren-9-One 11) Complex . Periódico Tchê Química.

2020; 17(34): 689-699.

*Bulk and Nanocatalysts Applications in Advanced Oxidation Processes DOI: http://dx.doi.org/10.5772/intechopen.94234*

Science and Engineering. 012132, IOP Publishing. 2018; 454(1): 1-11.

*Oxidoreductase*

2134-2140.

13-20.

101-111.

10(7):129-138.

[37] Mohammed B, and

[38] Jawad T. Synthesis and

[39] Fakhri F, and Ahmed L. Incorporation CdS with ZnS as

Characterization of Nano-Composite WO3/ TiO2 by Using Ultrasonic and it is Application on Photodecolorization of Eosin Yellow Dye [ MSC thesis]. Karbala: Kerbala University: 2020.

[32] Ahmed L. Photo-decolorization kinetics of acid red 87 dye in ZnO suspension under different types of UV-A light. Asian J. Chem. 2018; 30(9): nanocomposite and Using in Photo-Decolorization of Congo Red Dye. Indones. J. Chem.2019; 19(4):936-943.

Composites nano particles and using in photocatalytic-decolorization of Congo red dye[ MSC thesis]. Karbala: Kerbala

[41] Mashkour M, Al-Kaim A, Ahmed L, and Hussein F. Zinc Oxide Assisted Photocatalytic Decolourization of Reactive Red 2 Dye. Int. J. Chem. Sci.

Photocatalytic Decolourization of Direct Orange Dye by Zinc Oxide under UV Irradiation. Int. J. Chem. Sci.2015;

[40] Fakhri F. Preparation, Characterization of ZnS/CdS

University: 2019.

2011; 9(3): 969-979.

13(1):187-196.

1294(5):1-8.

[42] Zuafuani S, and Ahmed L.

[43] Ahmed L, Tawfeeq F, Abed Al-Ameer F, Abed Al-Hussein K. and Athaab A. Photo-Degradation of Reactive Yellow 14 Dye (A Textile Dye) Employing ZnO as Photocatalyst. Journal of Geoscience and Environment

Protection.2016; 4: 34-44.

[44] Abbas S, Hassan Z, and Ahmed L. Influencing the Artificial UV-A light on decolorization of Chlorazol black BH Dye via using bulk ZnO Suspensions. In Journal of Physics: Conference Series. IOP Publishing. 052050. 2019;

[45] Eesa M, Juda A, and Ahmed L. Kinetic and thermodynamic study of the photocatalytic decolourization of light green SF yellowish (acid green 5) dye using commercial bulk Titania and commercial Nanotitania. Int. J. Sci.

Res.2016; 5(11): 1495-1500.

[46] Hussein Z, Abbas S, and Ahmed, L. UV-A activated ZrO2 via photodecolorization of methyl green dye. In IOP Conference Series: Materials

[33] Pare B, Singh P and Jonnalagadda S, Visible Light-drive Photocatalytic Degradation and Minieralization of neutral Red dye in a sulurry

Photoreactor. Indian Journal Chemistry

Technoogy.2010; 17: 391-395.

[35] Fadhil F, Ahmed L, and

Mohammed A. Effect of silver doping on structural and photocatalytic circumstances of ZnO nanoparticles. Iraqi Journal of Nanotechnolog, Synthesis and Application. 2020; 1:

[36] Mahammed B, and Ahmed L. Enhanced Photocatalytic Properties of Pure and Cr-Modified ZnS

Ahmed L. Improvement the Photo Catalytic Properties of ZnS nanoparticle with Loaded Manganese and Chromium by Co-Precipitation Method. Journal of Global Pharma Technology. 2018;

Powders Synthesized by Precipitation Method. Journal of Geoscience and Environment Protection. 2017; 5:

[34] Jasim K, and Ahmed L. TiO2 Nanoparticles Sensitized by Safranine O Dye using UV-A Light System. In IOP Conference Series. Materials Science and Engineering. 2019; 571(012064):1-9.

**120**

[47] Hayawi M, Kareem M, and Ahmed L. Synthesis of Spinel Mn3O4 and Spinel Mn3O4/ZrO2 Nanocomposites and Using Them in Photo-Catalytic Decolorization of Fe(II)-(4,5-Diazafluoren-9-One 11) Complex . Periódico Tchê Química. 2020; 17(34): 689-699.

**123**

enzyme

**1. Introduction**

**1.1 Enzymes**

**Chapter 8**

**Abstract**

*Hussein Mahdi Kareem*

Oxidoreductases: Significance for

Oxidoreductases consist of a large class of enzymes catalyzing the transfer of electrons from an electron donor (reductant) to an electron acceptor (oxidant) molecule. Since so many chemical and biochemical transformations comprise oxidation/reduction processes, it has long been an important goal in biotechnology to develop practical biocatalytic applications of oxidoreductases. During the past few years, significant breakthrough has been made in the development of oxidoreductase-based diagnostic tests and improved biosensors, and the design of innovative systems for the regeneration of essential coenzymes. Research on the construction of bioreactors for pollutants biodegradation and biomass processing, and the development of oxidoreductase-based approaches for synthesis of polymers and functionalized organic substrates have made great progress. Proper names of oxidoreductases are in a form of "donor:acceptor oxidoreductase"; while in most cases "donor dehydrogenase" is much more common. Common names also sometimes appeared as "acceptor reductase", such as NAD+ reductase. "Donor oxidase" is a special case when O2 serves as the acceptor. In biochemical reactions, the redox reactions are sometimes more difficult to observe, such as this reaction from glycolysis:

where NAD+ is the oxidant (electron acceptor), and glyceraldehyde-3-phosphate

Are biotic chemical agents that rise the amount of biochemical reaction by depressing of activate energy. The particles convoluted in the enzyme intermediated responses is identified as substrate and the outcome of the reactions or produce are termed products. In general, the chemical structure of greatest for more enzymes is protein and hardly ever of other type e.g., Ribonucleic acid (RNA). The enzyme is too special on the way to their substrates of whom they re-join and thereby the reaction will also be so specific. At times the enzymes requests the turnout of a un protein part called coenzyme, if was a vitamin derivative Organic

**Keywords:** oxidoreductases, important of enzyme, application medical of this

+ 1,3-bisphosphoglycerate,

Humans and Microorganism

Pi + glyceraldehyde-3-phosphate + NAD+ → NADH + H+

functions as reductant (electron donor).

#### **Chapter 8**
