**1. Introduction**

In the late nineteenth century, Goddard Institute for Space Studies (GISS) found that global temperature is increasing on account of global warming at least 0.8°C in every year since 1951, which is continuing to increase still twenty-first century because of the release of greenhouse gases [1]. Based on such criteria "*The Intergovernmental Panel on Climate Change*" (IPCC)

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. © 2018 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.

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons

declares that this excessive CO2 emission is markedly related to global climate change and hence could adversely affect global temperature [2]. Furthermore, studies reveal that compared to the CO2 level of 280 ppm during pre-industrial era, CO2 concentration increases to 401 ppm in 2015, mainly because of human activity and anthropogenic industrial revolution that needs an ultimatum to check the atmospheric CO2 level [3]. Thus, in order to diminish carbon level, CO2 capture and storage/sequestration (CCS) as well as CO<sup>2</sup> capture and utilization (CCU) should have been implemented for considering a ultra-low carbon content environment. Regarding CCS processes, physical adsorption, absorption and membrane separation technologies are being involved to store CO2 in adsorbents which later buried in deep underground. As for instances, liquid amines like monoethanolamine and diethanolamine are traditionally being utilized to store CO2 through CCS processes [4], however, despite the wide use of such methods, it suffers from major drawbacks like corrosive nature and volatility of amines, decomposition of the generated salts as well as expensive regeneration cost [5]. Therefore, the requirement of new supports e.g.; porous organic polymers (POPs) [6], metal organic frameworks (MOFs) [7], zeolites [8], zeolitic imidazolate frameworks (ZIF) [9], microporous carbon [10], perovskites, hydrotalcites, clathrate hydrates [11], etc. are mandatory to overcome such drawbacks. It is worth mentioning, porous materials with suitably decorated narrow micropores/ultra narrow micropores are significant in adsorbing large quantity of CO<sup>2</sup> through utilization of hollow nanospace, hence, these materials could be promising in frontier research in order to check the adverse effect of CO<sup>2</sup> that is continuously releasing as tens of billions of tons in each year. Again, MOFs, POPs etc. having wide diversity in structure engineering, can stabilize various organometallic complexes through utilization of their surface functional sites, which in turn enhances their CO2 adsorption efficacy. Although CCS has wide applications, but only storage in nanopores could partially solve the carbon emission problems because underground leaking cannot be completely ruled out. This circumstance justifies the implementation of suitable process that could simultaneously convert the captured CO2 to value-added products [12]. Nevertheless, being cheap and easy availability, CO2 is enriched as C1 feedstock and has broad scope of serving as C1 chemistry to produce important products e.g. fuels, commodity chemicals, agrochemicals, valuable materials and so on [13].

coordination polymers because of their propensity to build up by metal atoms (ions) linked together by multifunctional organic ligands. Therefore, MOFs synthesis is a consequence of the linkage between the inorganic and organic chemistry, and it has been considered that MOFs are pioneered by Hagrman et al. [15], Batten and Robson [16], Zhou and Kitagawa

It is customary to say that the framework components of MOFs are required to precisely con-

oxy fuel combustion and potentially even for the specific power plant in which the capture system is to be installed. In this regard, significant efforts have been made recently in improving the gas separation performances of MOFs and some studies are therefore being under consideration for evaluating the prospects of deploying these materials in real-world CO2

ture [19]. This has been predominately invented by Noro et al. [20] and Yaghi et al. [18]. The wide diversity in its structure makes it possible to construct material with high surface area [21], tailor the material properties and thus its affinity towards specific gas molecules [22, 23]. Accordingly, it would be possible to develop MOF-based sorbents with large capacity and

It can be stated that most of the MOFs are synthesized using non-renewable organic solvents like N,N-dimethylformamide, dioxane, etc., although few MOFs (CD-MOF) can also be made from green solvents like ethanol, water etc. [27]. During synthesis, high surface area MOFs

solvent inside the pores are required to remove without any disturbance in its porous structure. However, special care must be taken to assure that the structure does not collapse. It is worthy to mention that the thermal stability of the MOF is expected to be lower than that of zeolites/zeolite analogues because MOFs have lower metal-linker binding energy than that of zeolites having stronger Si-O, Al-O linkages. In **Figure 1**, some representative MOF structures

storage capacity of MOFs is being measured at different temperature and pres-

uptake capacity. Among several MOFs, MOFs with square

(adenine)2


(bio-MOF-11) [26],

sure. There has also been established a positive connection between storage capacity and surface area at high pressure. Yaghi et al. [18] were first to explain the relationship

storage purposes.

are filled with solvent molecules. Since MOFs are being used for CO<sup>2</sup>

**Figure 1.** Crystal structure of several MOFs, e.g.; MOF-5 [24], DA-MOF [25], CO2

capture e.g. post-combustion capture, pre-combustion capture,

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cap-

167

storage, therefore, the

[17] and Yaghi et al. [18].

trol for specific type of CO<sup>2</sup>

high selectivity for CO2

are shown.

between surface area and CO2

with permission from respective references.

The CO2

In this chapter, we describe the fabrication of several important solid materials for controlling environmental remediation of CO2 through CCS techniques and also highlight their potential utility for CO2 adsorption purposes. However, our major aim is to focus the profound application and usage of several solid-phase adsorbents like, MOFs, POPs, nanoporous carbon, porous clays for CO2 capture and sequestration study.

#### **2. Promising materials for CO2 capture**

#### **2.1. Metal-organic frameworks (MOF)**

MOFs constitute of a new class of materials which could serve as an ideal platform for the development of next-generation CO2 capture materials because of their large capacity for adsorption of gases and easy tailorability of their structures [14]. MOFs are also called coordination polymers because of their propensity to build up by metal atoms (ions) linked together by multifunctional organic ligands. Therefore, MOFs synthesis is a consequence of the linkage between the inorganic and organic chemistry, and it has been considered that MOFs are pioneered by Hagrman et al. [15], Batten and Robson [16], Zhou and Kitagawa [17] and Yaghi et al. [18].

declares that this excessive CO2

166 Carbon Dioxide Chemistry, Capture and Oil Recovery

that needs an ultimatum to check the atmospheric CO2

ration technologies are being involved to store CO2

research in order to check the adverse effect of CO<sup>2</sup>

functional sites, which in turn enhances their CO2

environmental remediation of CO2

**2. Promising materials for CO2**

**2.1. Metal-organic frameworks (MOF)**

the development of next-generation CO2

utility for CO2

porous clays for CO2

are traditionally being utilized to store CO2

pared to the CO2

carbon level, CO2

emission is markedly related to global climate change and

concentration increases to

capture and uti-

to

is enriched as

level [3]. Thus, in order to diminish

in adsorbents which later buried in deep

that is continuously releasing as tens of

adsorption efficacy. Although CCS has wide

through CCS techniques and also highlight their potential

capture materials because of their large capacity

through CCS processes [4], however, despite the

hence could adversely affect global temperature [2]. Furthermore, studies reveal that com-

401 ppm in 2015, mainly because of human activity and anthropogenic industrial revolution

capture and storage/sequestration (CCS) as well as CO<sup>2</sup>

lization (CCU) should have been implemented for considering a ultra-low carbon content environment. Regarding CCS processes, physical adsorption, absorption and membrane sepa-

underground. As for instances, liquid amines like monoethanolamine and diethanolamine

wide use of such methods, it suffers from major drawbacks like corrosive nature and volatility of amines, decomposition of the generated salts as well as expensive regeneration cost [5]. Therefore, the requirement of new supports e.g.; porous organic polymers (POPs) [6], metal organic frameworks (MOFs) [7], zeolites [8], zeolitic imidazolate frameworks (ZIF) [9], microporous carbon [10], perovskites, hydrotalcites, clathrate hydrates [11], etc. are mandatory to overcome such drawbacks. It is worth mentioning, porous materials with suitably decorated narrow micropores/ultra narrow micropores are significant in adsorbing large quantity of CO<sup>2</sup> through utilization of hollow nanospace, hence, these materials could be promising in frontier

billions of tons in each year. Again, MOFs, POPs etc. having wide diversity in structure engineering, can stabilize various organometallic complexes through utilization of their surface

applications, but only storage in nanopores could partially solve the carbon emission problems because underground leaking cannot be completely ruled out. This circumstance justifies the implementation of suitable process that could simultaneously convert the captured CO2

C1 feedstock and has broad scope of serving as C1 chemistry to produce important products

In this chapter, we describe the fabrication of several important solid materials for controlling

cation and usage of several solid-phase adsorbents like, MOFs, POPs, nanoporous carbon,

MOFs constitute of a new class of materials which could serve as an ideal platform for

for adsorption of gases and easy tailorability of their structures [14]. MOFs are also called

 **capture**

adsorption purposes. However, our major aim is to focus the profound appli-

value-added products [12]. Nevertheless, being cheap and easy availability, CO2

capture and sequestration study.

e.g. fuels, commodity chemicals, agrochemicals, valuable materials and so on [13].

level of 280 ppm during pre-industrial era, CO2

It is customary to say that the framework components of MOFs are required to precisely control for specific type of CO<sup>2</sup> capture e.g. post-combustion capture, pre-combustion capture, oxy fuel combustion and potentially even for the specific power plant in which the capture system is to be installed. In this regard, significant efforts have been made recently in improving the gas separation performances of MOFs and some studies are therefore being under consideration for evaluating the prospects of deploying these materials in real-world CO2 capture [19]. This has been predominately invented by Noro et al. [20] and Yaghi et al. [18]. The wide diversity in its structure makes it possible to construct material with high surface area [21], tailor the material properties and thus its affinity towards specific gas molecules [22, 23]. Accordingly, it would be possible to develop MOF-based sorbents with large capacity and high selectivity for CO2 storage purposes.

It can be stated that most of the MOFs are synthesized using non-renewable organic solvents like N,N-dimethylformamide, dioxane, etc., although few MOFs (CD-MOF) can also be made from green solvents like ethanol, water etc. [27]. During synthesis, high surface area MOFs are filled with solvent molecules. Since MOFs are being used for CO<sup>2</sup> storage, therefore, the solvent inside the pores are required to remove without any disturbance in its porous structure. However, special care must be taken to assure that the structure does not collapse. It is worthy to mention that the thermal stability of the MOF is expected to be lower than that of zeolites/zeolite analogues because MOFs have lower metal-linker binding energy than that of zeolites having stronger Si-O, Al-O linkages. In **Figure 1**, some representative MOF structures are shown.

The CO2 storage capacity of MOFs is being measured at different temperature and pressure. There has also been established a positive connection between storage capacity and surface area at high pressure. Yaghi et al. [18] were first to explain the relationship between surface area and CO2 uptake capacity. Among several MOFs, MOFs with square

**Figure 1.** Crystal structure of several MOFs, e.g.; MOF-5 [24], DA-MOF [25], CO2 (adenine)2 -(CH3 CO2 ) 2 (bio-MOF-11) [26], with permission from respective references.

channels (MOF-2) [28], pores with open metal sites (MOF-505, Cu3 (BTC)2 ) [29], interpenetrated (IRMOF-11) [29], CO2 (adenine)2 -(CH3 CO2 )2 functionalized bio-MOF-11 are interesting [30]. It is important to mention that MOF-177 has the high surface area (4500 m2 g−1) and possesses high uptake of CO2 (60 wt% at 35 bar) at high pressure. Very recently, ultrahigh porous MOFs are prepared by Furukawa et al. from Zn4 O(CO2 )6 unit, containing one or two organic linkers and among them MOF-210 showed highest BET surface area (6240 m2 g−1) and high pore volume (3.6 cm3 g−1) reported till date [31]. The ultrahigh porosity of MOF-210 has been achieved mainly because of the expanding organic linkers. As for instance, by extending the size of the 1,3,5-benzenetribenzoate (BTC) in MOF-177 by replacing with larger 4,4′,4″-(benzene-1,3,5- triyl-tris(benzene-4,1-iyl)) tribenzoate (BBC), MOF-200 was obtained with even higher BET than that of MOF-177 [32]. Strikingly, MOF-210 and MOF-200 show ~71 wt% CO2 uptake capacity at 298 K and 50 bar pressure, which are highest and considered as new record among all solid porous materials. For CO2 capture at ambient condition as well as flue gas condition, CO<sup>2</sup> capture is not only influenced by surface area but is also dependent on adsorbent-CO2 interaction. In this context, Mg-MOF-74 [Mg2 (DOT); DOT: 2,5-dioxidoterephthalate] consisting of an open framework with Mg2+ sites shows high CO2 storage capacity of 35.2 wt% at 298 K and 1 bar [32]. It is pertinent to mention that open metal sites are mandatory in achieving high CO2 storage capacity. In **Table 1**, we present some MOFs having significance in CO<sup>2</sup> capture at low and high pressure.

On the other hand, thermal degradation of MOFs generally happens on account of metal-ligand bond breaking. As a consequence, thermal stability of MOFs is predominately dependent on both the metal-linker bond strength and the number of linkers connected to metal sites. Indeed, MOFs can be stable up to 300°C without degradation of the framework structure [17, 18], which

can easily coordinate to open metal sites. It has been found that in some cases small amount

water molecules coordinated to open metal sites of Cu-BTC (HKUST-1) and thus significantly

(M = Zn, Ni, Co and Mg; DOBC = 2,5-dioxidobenzene-1,4-dicarboxylate), demonstrating a

Liu et al. also described water stability of various MOFs after their pretreatment, further sug-

POPs are recently developed as an important class of porous materials, constructed from lightweight elements (C, H, O, N) and linked by strong covalent bonds, which show huge potential in a variety of applications, e.g.; gas storage and separation, catalysis, sensing, energy storage, optoelectronics and to mention a few [8, 47–49]. A series of vibrant characteristics of POPs, such as high-specific surface area, good physicochemical stability, tunable pore dimensions, topolo-

POPs are widely used and have been classified according to their synthesis conditions, which includes polymers of intrinsic microporosity (PIMs), conjugated microporous polymers (CMPs), covalent organic polymers, hypercrosslinked polymers (HCPs), crystalline triazinebased frameworks (CTFs), porous organic frameworks (POFs), porous aromatic frameworks (PAFs), polymeric organic networks (PONs) and so on. In each networks, the state-of-the art

also be controlled through manipulation of POP surface area, pore size and/or its functionality at the surfaces. Understanding all these aspects could lead to the development of new

teristics, high cross-linked ultra-microporous structures could be crucial in determining CO2 adsorption performances. Herein, we describe the critical factors that directly influence the

There is a direct correlation between POP surface area and its porous structures. It is said

uptake of an adsorbent increases with increasing CO2

onstrates that controlling of surface property might be advantageous in tailoring CO2

uptake capacity is dependent on the high specific surface area. It has also been sug-

adsorption of this framework [33]. However, in other cases; water could only

capture from flue gas under moist conditions.

adsorption in some MOFs. Yazaydin et al. have observed that

uptake capacities for Mg/DOBC and Zn/DOBC [34]. Recently,

capture performance of M/DOBDC series of MOFs

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uptake property, one common

uptake because water

169

adsorption. Kizzie et al.

capture.

adsorption performances

pressure, which dem-

uptake

uptake capacity and adsorption enthalpy can

capture, where the amorphous charac-

is crucial for post-combustion CO2

of water can accelerate CO2

significant decrease in the CO<sup>2</sup>

**2.2. Porous organic polymers (POP)**

showed the effect of humidity on the CO<sup>2</sup>

gesting their stability in aqueous condition [35].

has been reviewed [50, 51]. Additionally, CO2

uptake property for POPs.

possibilities of novel POP frameworks to target CO2

increase CO2

CO2

that CO2

gested that CO2

Since open metal sites in MOFs show considerably good CO2

question that may rise among readers is the effect of water on CO<sup>2</sup>

destroy the MOF structure and shows a detrimental effect on CO<sup>2</sup>

gies and chemical functionalities, make them suitable adsorbents for CO2

development in the design, synthesis, characterization and the CO2


**Table 1.** CO2 adsorption capacity of metal-organic frameworks at low and high pressure. On the other hand, thermal degradation of MOFs generally happens on account of metal-ligand bond breaking. As a consequence, thermal stability of MOFs is predominately dependent on both the metal-linker bond strength and the number of linkers connected to metal sites. Indeed, MOFs can be stable up to 300°C without degradation of the framework structure [17, 18], which is crucial for post-combustion CO2 capture from flue gas under moist conditions.

Since open metal sites in MOFs show considerably good CO2 uptake property, one common question that may rise among readers is the effect of water on CO<sup>2</sup> uptake because water can easily coordinate to open metal sites. It has been found that in some cases small amount of water can accelerate CO2 adsorption in some MOFs. Yazaydin et al. have observed that water molecules coordinated to open metal sites of Cu-BTC (HKUST-1) and thus significantly increase CO2 adsorption of this framework [33]. However, in other cases; water could only destroy the MOF structure and shows a detrimental effect on CO<sup>2</sup> adsorption. Kizzie et al. showed the effect of humidity on the CO<sup>2</sup> capture performance of M/DOBDC series of MOFs (M = Zn, Ni, Co and Mg; DOBC = 2,5-dioxidobenzene-1,4-dicarboxylate), demonstrating a significant decrease in the CO<sup>2</sup> uptake capacities for Mg/DOBC and Zn/DOBC [34]. Recently, Liu et al. also described water stability of various MOFs after their pretreatment, further suggesting their stability in aqueous condition [35].

### **2.2. Porous organic polymers (POP)**

channels (MOF-2) [28], pores with open metal sites (MOF-505, Cu3

ultrahigh porous MOFs are prepared by Furukawa et al. from Zn4

capture at ambient condition as well as flue gas condition, CO<sup>2</sup>

enced by surface area but is also dependent on adsorbent-CO2


esting [30]. It is important to mention that MOF-177 has the high surface area (4500 m2 g−1)

ing one or two organic linkers and among them MOF-210 showed highest BET surface area (6240 m2 g−1) and high pore volume (3.6 cm3 g−1) reported till date [31]. The ultrahigh porosity of MOF-210 has been achieved mainly because of the expanding organic linkers. As for instance, by extending the size of the 1,3,5-benzenetribenzoate (BTC) in MOF-177 by replacing with larger 4,4′,4″-(benzene-1,3,5- triyl-tris(benzene-4,1-iyl)) tribenzoate (BBC), MOF-200 was obtained with even higher BET than that of MOF-177 [32]. Strikingly,

which are highest and considered as new record among all solid porous materials. For CO2

pertinent to mention that open metal sites are mandatory in achieving high CO2

MOF-177 4500 60 298 50 [31] MOF-210 6240 71 298 50 [31] Mg-MOF-74 1640 35.2 298 1 [32]

(abtc)3 — 38.5 273 1 [36] Dy(BTC) 655 27.2 273 1 [37]

(BTetB) 1370 19.7 273 1 [39]

(bptb) 1217 12.6 273 1 [43]

(BTetB)(DMF)2 800 12.1 273 1 [30]

(BDoborDC)4 800 12.1 273 1 [44]

Cd(mim)2 2420 5.6 273 1 [46]

adsorption capacity of metal-organic frameworks at low and high pressure.

(p-CDC)3 1080 16.4 273 1 [41]

)2 — 13.8 273 1 [42]

)2 — 11.9 273 1 [34]

)4 — 10.6 273 1 [45]

capacity. In **Table 1**, we present some MOFs having significance in CO<sup>2</sup>

(DOT); DOT: 2,5-dioxidoterephthalate] consisting of an open framework

)3 1268 24.1 273 1 [38]

) 892 17.9 273 1 [40]

storage capacity of 35.2 wt% at 298 K and 1 bar [32]. It is

CO2 )2

etrated (IRMOF-11) [29], CO2 (adenine)2

MOF-210 and MOF-200 show ~71 wt% CO2

**Chemical formulae BET (m2 g−1) CO2**

Mg-MOF-74 [Mg2

high pressure.

(OCH3 )4 (BDC-NH2

O(diazDBC)1.5(H2

(BF4

(BF4

O)3 ](NO3

Cu2

Al4 (OH)2

Zn2

[In3

Co4 (OH)2

Cu2

Zn2

Zn2

Ni2 (bpy)3 (NO3

Ni(bpy)2

**Table 1.** CO2

Cu(bpy)2

with Mg2+ sites shows high CO2

and possesses high uptake of CO2

168 Carbon Dioxide Chemistry, Capture and Oil Recovery

(BTC)2

functionalized bio-MOF-11 are inter-

O(CO2 )6

uptake capacity at 298 K and 50 bar pressure,

 **storage (wt%) Temp. (K) Pressure (bar) References**

capture is not only influ-

interaction. In this context,

(60 wt% at 35 bar) at high pressure. Very recently,

) [29], interpen-

unit, contain-

storage

capture at low and

POPs are recently developed as an important class of porous materials, constructed from lightweight elements (C, H, O, N) and linked by strong covalent bonds, which show huge potential in a variety of applications, e.g.; gas storage and separation, catalysis, sensing, energy storage, optoelectronics and to mention a few [8, 47–49]. A series of vibrant characteristics of POPs, such as high-specific surface area, good physicochemical stability, tunable pore dimensions, topologies and chemical functionalities, make them suitable adsorbents for CO2 capture.

POPs are widely used and have been classified according to their synthesis conditions, which includes polymers of intrinsic microporosity (PIMs), conjugated microporous polymers (CMPs), covalent organic polymers, hypercrosslinked polymers (HCPs), crystalline triazinebased frameworks (CTFs), porous organic frameworks (POFs), porous aromatic frameworks (PAFs), polymeric organic networks (PONs) and so on. In each networks, the state-of-the art development in the design, synthesis, characterization and the CO2 adsorption performances has been reviewed [50, 51]. Additionally, CO2 uptake capacity and adsorption enthalpy can also be controlled through manipulation of POP surface area, pore size and/or its functionality at the surfaces. Understanding all these aspects could lead to the development of new possibilities of novel POP frameworks to target CO2 capture, where the amorphous characteristics, high cross-linked ultra-microporous structures could be crucial in determining CO2 adsorption performances. Herein, we describe the critical factors that directly influence the CO2 uptake property for POPs.

There is a direct correlation between POP surface area and its porous structures. It is said that CO2 uptake capacity is dependent on the high specific surface area. It has also been suggested that CO2 uptake of an adsorbent increases with increasing CO2 pressure, which demonstrates that controlling of surface property might be advantageous in tailoring CO2 uptake phenomenon. Significant development in the synthesis of high surface area POP materials has been done by several researchers, among which the synthesis of porous aromatic framework (PAF-1) developed by Qiu et al. via Yamamoto homocoupling of tetrahedral monomers (tetrakis(4-bromophenyl)methane) is significant [52]. Owing to the in-build generation of diamondoid framework topology by the cross-linking of tetrahedral monomers, it creates open and interconnected pores which give rise to high surface area (BET: 5600 m2 g−1) and good CO2 storage capacity (29.5 mmol g−1, 298 K, 40 bar). Later significant contribution has been developed by modifying with other quadricovalent building centers [53], which forms PPN-3 (with adamantine-system), PPN-4 (replaced tetrahedral carbon by silicon) and PPN-5 (replaced tetrahedral carbon by Germanium), as shown in **Figure 2**. Importantly, all these POPs possess exceptionally high surface area. It should be noted that PPN-4 having BET surface area of 6461 m2 g−1 considers as highest surface area among all reported POPs till date. The exceptionally high surface area enables PPN-4 to have excellent CO2 storage capacity (48.2 mmol g−1) at 50 bar and 295 K.

et al., where the knitting polymerization has been utilized for binding tetraphenyl aromatic moieties (**Figure 4**) [56]. Unlike the conventional Suzuki/Sonogashira coupling reactions, HCP polymerization promotes the cross-linking between tetrahedral aromatic moieties in a facile way. In continuation with this research, silicon (Si) and germanium (Ge) containing

Friedel − Crafts alkylation between tetraphenylsilane or tetraphenylgermanium as a building block and formaldehyde dimethyl acetal as a cross-linker, which yields high surface area

with an isosteric heat of adsorption in the range of 26.5–27.3 kJ mol−1 (**Figure 4**). It is worthy to mention that controlled synthesis of silicon and germanium-based nanoscale POPs is very difficult and shows intense research activities because Si and Ge are crucial in influencing

ever, it is not the prime reason, indeed adsorbate-adsorbent interaction might be quite effec-

other gases. In this regard, N, P, O, S etc. atoms when incorporated into POPs, show dramatic change in adsorption capacity as well as in the selectivity; because heteroatoms can improve

**Figure 4.** Synthesis of porous hypercrosslinked aromatic polymers (PHAP) containing central hetero atoms Si, Ge other

than carbon. CO2 uptake capacity is given at the right; reproduced with permission from Ref. [56].

pressure and for selective adsorption of CO2

mediated

171

adsorption capacity (104.3–114.4 mg g−1)

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adsorption behavior, how-

in presence of

nanoscale hyper-cross-linked aromatic polymers (PHAPs) were reported by FeCl3

**Figure 3.** Schematic representation of the formation of hypercrosslinked porous polymers.

(1137–1059 m2 g−1) stable polymers having high CO2

Although high BET surface area is necessary for influencing CO<sup>2</sup>

physical properties of these POPs.

tive for adsorption at low CO2

Therefore, it can be arguably said that the design followed by the synthesis of high surface area POPs from tetrahedral building block is a promising approach for CO2 storage at high pressure. Apart from BET surface area, porous structure also triggers CO2 uptake phenomenon, as controlling the pore size similar to the kinetic diameter of CO2 molecule (Size: 3.3 Å) can significantly enhance the storage capacity. So far many researches have been made significant effort to make POPs from tetrahedral building units as CO<sup>2</sup> adsorbents and among them hypercrosslinked (HCPs) amorphous polymers are important. HCPs exhibit unique property in gas storage capacity due to its highly cross-linked network which prevents the interconnected porous frameworks from being collapsed [54]. In **Figure 3**, the formation of cross-linked HCP is presented.

The unique advantage for the synthesis of HCPs, possesses huge prospect in materials chemistry research because it requires cheap, readily available precursors and FeCl<sup>3</sup> as nontoxic catalyst. Therefore, utilizing this procedure, several aromatic polymers can be easily prepared as described by Cooper et al. [55] In presence of 1,1′-binapthol the resulting HCP shows 1015 m2 g−1 BET surface area with high CO2 uptake capacity (3.96 mmol g−1, 1 bar). The high CO2 capture capacity is hardly affected by aqueous environment owing to strong hydrophobicity of HCPs. Another interesting research has been done by Puthiaraj

**Figure 2.** Synthetic routes for high surface area PPN-4 (X: Si), PPN-5 (X: Ge), PAF-1 (X: C) from tetrahedral building blocks.

**Figure 3.** Schematic representation of the formation of hypercrosslinked porous polymers.

phenomenon. Significant development in the synthesis of high surface area POP materials has been done by several researchers, among which the synthesis of porous aromatic framework (PAF-1) developed by Qiu et al. via Yamamoto homocoupling of tetrahedral monomers (tetrakis(4-bromophenyl)methane) is significant [52]. Owing to the in-build generation of diamondoid framework topology by the cross-linking of tetrahedral monomers, it creates open and interconnected pores which give rise to high surface area (BET: 5600 m2 g−1) and

been developed by modifying with other quadricovalent building centers [53], which forms PPN-3 (with adamantine-system), PPN-4 (replaced tetrahedral carbon by silicon) and PPN-5 (replaced tetrahedral carbon by Germanium), as shown in **Figure 2**. Importantly, all these POPs possess exceptionally high surface area. It should be noted that PPN-4 having BET surface area of 6461 m2 g−1 considers as highest surface area among all reported POPs till date.

Therefore, it can be arguably said that the design followed by the synthesis of high surface

can significantly enhance the storage capacity. So far many researches have been made sig-

them hypercrosslinked (HCPs) amorphous polymers are important. HCPs exhibit unique property in gas storage capacity due to its highly cross-linked network which prevents the interconnected porous frameworks from being collapsed [54]. In **Figure 3**, the formation of

The unique advantage for the synthesis of HCPs, possesses huge prospect in materials

toxic catalyst. Therefore, utilizing this procedure, several aromatic polymers can be easily prepared as described by Cooper et al. [55] In presence of 1,1′-binapthol the resulting

strong hydrophobicity of HCPs. Another interesting research has been done by Puthiaraj

**Figure 2.** Synthetic routes for high surface area PPN-4 (X: Si), PPN-5 (X: Ge), PAF-1 (X: C) from tetrahedral building

capture capacity is hardly affected by aqueous environment owing to

chemistry research because it requires cheap, readily available precursors and FeCl<sup>3</sup>

The exceptionally high surface area enables PPN-4 to have excellent CO2

area POPs from tetrahedral building block is a promising approach for CO2

pressure. Apart from BET surface area, porous structure also triggers CO2

enon, as controlling the pore size similar to the kinetic diameter of CO2

nificant effort to make POPs from tetrahedral building units as CO<sup>2</sup>

HCP shows 1015 m2 g−1 BET surface area with high CO2

storage capacity (29.5 mmol g−1, 298 K, 40 bar). Later significant contribution has

storage capacity

storage at high

as non-

uptake phenom-

molecule (Size: 3.3 Å)

adsorbents and among

uptake capacity (3.96 mmol g−1,

good CO2

(48.2 mmol g−1) at 50 bar and 295 K.

170 Carbon Dioxide Chemistry, Capture and Oil Recovery

cross-linked HCP is presented.

1 bar). The high CO2

blocks.

et al., where the knitting polymerization has been utilized for binding tetraphenyl aromatic moieties (**Figure 4**) [56]. Unlike the conventional Suzuki/Sonogashira coupling reactions, HCP polymerization promotes the cross-linking between tetrahedral aromatic moieties in a facile way. In continuation with this research, silicon (Si) and germanium (Ge) containing nanoscale hyper-cross-linked aromatic polymers (PHAPs) were reported by FeCl3 mediated Friedel − Crafts alkylation between tetraphenylsilane or tetraphenylgermanium as a building block and formaldehyde dimethyl acetal as a cross-linker, which yields high surface area (1137–1059 m2 g−1) stable polymers having high CO2 adsorption capacity (104.3–114.4 mg g−1) with an isosteric heat of adsorption in the range of 26.5–27.3 kJ mol−1 (**Figure 4**). It is worthy to mention that controlled synthesis of silicon and germanium-based nanoscale POPs is very difficult and shows intense research activities because Si and Ge are crucial in influencing physical properties of these POPs.

Although high BET surface area is necessary for influencing CO<sup>2</sup> adsorption behavior, however, it is not the prime reason, indeed adsorbate-adsorbent interaction might be quite effective for adsorption at low CO2 pressure and for selective adsorption of CO2 in presence of other gases. In this regard, N, P, O, S etc. atoms when incorporated into POPs, show dramatic change in adsorption capacity as well as in the selectivity; because heteroatoms can improve

**Figure 4.** Synthesis of porous hypercrosslinked aromatic polymers (PHAP) containing central hetero atoms Si, Ge other than carbon. CO2 uptake capacity is given at the right; reproduced with permission from Ref. [56].

isosteric heat of adsorption between sorbent and sorbate. To address this issues POPs with different functional sites e.g. pyridine (PON-2) or thiophene (PON-3) have been prepared, which exhibit favorable interaction with CO2 despite of having low surface areas [PON-2 (189 m2 g−1) and PON-3 (44 m2 g−1)] than only phenyl-based PON (BET 1447 m2 g−1), clearly explaining the effect of hetero-atom in POP structure [57]. Based on this proposal, a variety of N-containing POPs with several functional sites e.g. carbazole, triazine, porphyrin, benzimidazole, azo, etc. have been reported by several researchers as discussed in the subsequent section.

and excellent adsorbent for CO2

**2.3. Porous clay materials**

als have been used for CO2

MSiNTs/PEI (MP) for CO2

bentonite, etc.

(6.2 mmol g−1 or 27.3 wt% at 3 bar, 273 K).

(19 wt%, 273 K, 1 atm; by Fe-POP-1), shown in **Figure 5**.

Advances in Porous Adsorbents for CO2 Capture and Storage

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173

capture, like halloysite, kaolinite, montmorillonite, nanosepiolite,

adsorption [66]. Recently, Jana and coworkers demonstrate the

This research has further been extended by changing aromatic dialdehydes to aromatic trialdehyde using 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)tris(oxy)tribenzaldehyde as tripodal precursor. The advantage of using this organic precursor is enormous, because it introduces both triazine and porphyrin networks in a single TPOP-1 material, which stores high amount of CO2

The key advantages of any porous materials involve flexible surface modification due to the availability of high surface area together with lower regeneration energy compared to the any conventional solvent methods. Among the several porous materials, clay minerals are one of the significant materials since they have unique physical properties because of their layered structure, small grain size and large surface to volume ratio. Apart from the mentioned advantages, clay possesses low cost, high mechanical and chemical stability that has been fascinated to the researchers and withdrawn specific research attention. A variety of clay miner-

In a recent report, pristine halloysite nanotubes (HNTs) were pretreated with acid for selective removal of alumina and thus, produce mesoporous silica nanotubes (MSiNTs), which were then impregnated with polyethylenimine (PEI) to prepare an emerging nanocomposite

development of several HNTs based solid adsorbents being grafted with diverse aminosilanes containing both primary and/or secondary amine sites over the surfaces of inexpensive

**Figure 5.** Schematic representation for the preparation of porphyrin-based porous polymers by electrophilic aromatic

substitution of pyrrole with several aromatic dialdehydes and trialdehydes.

Microporous polycarbazole (CPOP-1) through polymerization of carbazole has been prepared by Chen et al. by oxidative polymerization of carbazole with FeCl3 as cheap and non-toxic catalyst [58]. CPOP-1 shows high BET surface area (2220 m2 g−1), narrow pore size (0.62 nm) together with the presence of electron-rich carbazole units and high charge density at N-sites, which facilitate uptake of polarizable CO2 molecule through local dipole-quadrupole interactions. The CO2 uptake of CPOP-1 is as high as 4.8 mmol g−1 at 273 K and 1 bar, along with its high selectivity for CO2 /CH4 (33) and CO2 /N2 (25) separation is also noticeable on account of the framework composition. Consequently, they have also prepared CPOP-(2-7) through this reaction and among them CPOP-7 exhibits the best uptake capacity for CO2 (3 mmol g−1 at 273 K and 1 bar) [59]. Among other N-containing polymeric adsorbents, covalent triazine frameworks (CTFs) are interesting. CTFs are efficiently applied to CO<sup>2</sup> capture purposes and are generally synthesized at high temperature (>400°C) by molten ZnCl2 which usually acts as Lewis acid catalyst as well as solvents. CTFs possess moderate BET surface area (1235 m2 g−1), while showing excellent CO2 uptake capacity (4.2 mmol g−1, 1 atm, 273 K) [60]. Again, several PCTFs were synthesized through the modifications of CTFs using branched arms precursors. Importantly, PCTF-1 with biphenyl, PCTF-2 with terphenyl and PCTF-3 with quaterphenyl rings have been developed, which show BET surface area as 853, 811 and 395 m2 g−1 respectively [61]. When the middle benzene ring of CTF has been replaced by the strong polar group, such as benzothiadiazole, forming PCTF-4 which shows highest CO2 uptake of 4.7 mmol g−1 at 273 K and 1 bar. Later, Zou and others prepared a nitrogen-rich polysulfone/ polymer (PSF/SNW-1) membrane by introducing nano-sized SNW-1 particles through intrinsically small micropores into PSF matrix via spin-coating [62]. Gas sorption measurements demonstrated that SNW-1 exhibits high adsorption capacity and good affinity towards CO<sup>2</sup> because of its high microporosity and the presence of functional amino groups. For CO2 separation, it demonstrates an excellent separation performance including high separation factor (34 and 40 for CO2 /CH4 and CO2 /N2 ) and high CO2 permeability (22.4 barrer). Furthermore, long thermal stability is also noticeable and further satisfies that SNW-1/PSF membrane is stable and robust; exhibiting its potentiality in the practical application of CO2 capture.

Based on the above discussion, it is evident that the effect of N-substituted POPs markedly influence CO<sup>2</sup> adsorption and separation processes. Regarding this, porphyrin containing microporous POP shows potential application in this area. Porphyrin-based POPs are generally synthesized from expensive Pd and Ni catalysts by a tedious way [63]. However, Modak and Bhaumik introduced a new method with FeCl3 for the formation of porphyrin polymers through a one pot bottom up chemistry involving the condensation between pyrrole and several aromatic dialdehydes [64, 65]. In this report, authors reported the formation of Fe-POP-1/2/3 having 750–875 m2 g−1 BET surface area, narrow microporosity (0.75–1.1 nm) and excellent adsorbent for CO2 (19 wt%, 273 K, 1 atm; by Fe-POP-1), shown in **Figure 5**. This research has further been extended by changing aromatic dialdehydes to aromatic trialdehyde using 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)tris(oxy)tribenzaldehyde as tripodal precursor. The advantage of using this organic precursor is enormous, because it introduces both triazine and porphyrin networks in a single TPOP-1 material, which stores high amount of CO2 (6.2 mmol g−1 or 27.3 wt% at 3 bar, 273 K).

### **2.3. Porous clay materials**

isosteric heat of adsorption between sorbent and sorbate. To address this issues POPs with different functional sites e.g. pyridine (PON-2) or thiophene (PON-3) have been prepared, which

and PON-3 (44 m2 g−1)] than only phenyl-based PON (BET 1447 m2 g−1), clearly explaining the effect of hetero-atom in POP structure [57]. Based on this proposal, a variety of N-containing POPs with several functional sites e.g. carbazole, triazine, porphyrin, benzimidazole, azo, etc.

Microporous polycarbazole (CPOP-1) through polymerization of carbazole has been prepared

catalyst [58]. CPOP-1 shows high BET surface area (2220 m2 g−1), narrow pore size (0.62 nm) together with the presence of electron-rich carbazole units and high charge density at N-sites,

/N2

of the framework composition. Consequently, they have also prepared CPOP-(2-7) through

at 273 K and 1 bar) [59]. Among other N-containing polymeric adsorbents, covalent triazine

Lewis acid catalyst as well as solvents. CTFs possess moderate BET surface area (1235 m2 g−1),

PCTFs were synthesized through the modifications of CTFs using branched arms precursors. Importantly, PCTF-1 with biphenyl, PCTF-2 with terphenyl and PCTF-3 with quaterphenyl rings have been developed, which show BET surface area as 853, 811 and 395 m2 g−1 respectively [61]. When the middle benzene ring of CTF has been replaced by the strong

4.7 mmol g−1 at 273 K and 1 bar. Later, Zou and others prepared a nitrogen-rich polysulfone/ polymer (PSF/SNW-1) membrane by introducing nano-sized SNW-1 particles through intrinsically small micropores into PSF matrix via spin-coating [62]. Gas sorption measurements demonstrated that SNW-1 exhibits high adsorption capacity and good affinity towards CO<sup>2</sup> because of its high microporosity and the presence of functional amino groups. For CO2

ration, it demonstrates an excellent separation performance including high separation factor

long thermal stability is also noticeable and further satisfies that SNW-1/PSF membrane is

Based on the above discussion, it is evident that the effect of N-substituted POPs markedly

ing microporous POP shows potential application in this area. Porphyrin-based POPs are generally synthesized from expensive Pd and Ni catalysts by a tedious way [63]. However,

polymers through a one pot bottom up chemistry involving the condensation between pyrrole and several aromatic dialdehydes [64, 65]. In this report, authors reported the formation of Fe-POP-1/2/3 having 750–875 m2 g−1 BET surface area, narrow microporosity (0.75–1.1 nm)

adsorption and separation processes. Regarding this, porphyrin contain-

) and high CO2

uptake of CPOP-1 is as high as 4.8 mmol g−1 at 273 K and 1 bar, along with

have been reported by several researchers as discussed in the subsequent section.

by Chen et al. by oxidative polymerization of carbazole with FeCl3

(33) and CO2

frameworks (CTFs) are interesting. CTFs are efficiently applied to CO<sup>2</sup>

are generally synthesized at high temperature (>400°C) by molten ZnCl2

this reaction and among them CPOP-7 exhibits the best uptake capacity for CO2

polar group, such as benzothiadiazole, forming PCTF-4 which shows highest CO2

/CH4

despite of having low surface areas [PON-2 (189 m2 g−1)

molecule through local dipole-quadrupole interac-

uptake capacity (4.2 mmol g−1, 1 atm, 273 K) [60]. Again, several

(25) separation is also noticeable on account

permeability (22.4 barrer). Furthermore,

as cheap and non-toxic

(3 mmol g−1

uptake of

sepa-

capture purposes and

which usually acts as

capture.

for the formation of porphyrin

exhibit favorable interaction with CO2

172 Carbon Dioxide Chemistry, Capture and Oil Recovery

which facilitate uptake of polarizable CO2

tions. The CO2

its high selectivity for CO2

while showing excellent CO2

(34 and 40 for CO2

influence CO<sup>2</sup>

/CH4

and CO2

Modak and Bhaumik introduced a new method with FeCl3

/N2

stable and robust; exhibiting its potentiality in the practical application of CO2

The key advantages of any porous materials involve flexible surface modification due to the availability of high surface area together with lower regeneration energy compared to the any conventional solvent methods. Among the several porous materials, clay minerals are one of the significant materials since they have unique physical properties because of their layered structure, small grain size and large surface to volume ratio. Apart from the mentioned advantages, clay possesses low cost, high mechanical and chemical stability that has been fascinated to the researchers and withdrawn specific research attention. A variety of clay minerals have been used for CO2 capture, like halloysite, kaolinite, montmorillonite, nanosepiolite, bentonite, etc.

In a recent report, pristine halloysite nanotubes (HNTs) were pretreated with acid for selective removal of alumina and thus, produce mesoporous silica nanotubes (MSiNTs), which were then impregnated with polyethylenimine (PEI) to prepare an emerging nanocomposite MSiNTs/PEI (MP) for CO2 adsorption [66]. Recently, Jana and coworkers demonstrate the development of several HNTs based solid adsorbents being grafted with diverse aminosilanes containing both primary and/or secondary amine sites over the surfaces of inexpensive

**Figure 5.** Schematic representation for the preparation of porphyrin-based porous polymers by electrophilic aromatic substitution of pyrrole with several aromatic dialdehydes and trialdehydes.

and easily available HNTs to capture CO2 from the ambient air under room temperature and ambient pressure [67]. They have also explored the effect of relative humidity in terms of moisture on the adsorption kinetics of the adsorbents by carrying out the experiment on the seasonal ambient air [11], exhibiting that relative humidity basically regulates the atmospheric CO2 adsorption and corresponding adsorption kinetics (**Figure 6**). Jana et al. also studied the kinetics of several stable isotopes of CO2 present in the ambient air [68]. Schaef et al. reported the adsorption of CO2 onto kaolinite surfaces under geologic sequestration conditions and also verified through the density functional theory (DFT) [69]. Wang et al. developed montmorillonite supported PEI composite for CO2 capture [70]; the CO2 sorption efficacy was found to be 2.54 mmol g−1 under dry environmental condition and 3.23 mmol g−1 under moisture added condition. They also verified that the density of CO<sup>2</sup> in the clay pores is comparatively stable over a wide range of CO2 pressures at a given temperature and at the excess sorption maximum. CO2 sorption increases with decreasing temperature while the high pressure sorption properties demonstrate weak temperature dependence. Elliot A. Roth and coworkers synthesized amine-containing solid sorbent for CO2 capture through the modification of the surface of montmorillonite nanoclay using aminopropyltrimethoxysilane and polyethylenimine [71]. They found that in pure CO2 and 10% CO2 in nitrogen gas streams the nanoclay loaded with only one of the amines exhibits ~6 wt% capture efficacy at 85°C and atmospheric pressure, whereas it is ~7.5 wt% CO<sup>2</sup> capture efficiency when the nanoclay immobilized with both the amines. Irani et al. utilized nanosepiolite as an inorganic-organic CO2 sorbent by immobilizing tetraethylenepentamine (TEPA) onto acidmodified nanosepiolite, having capacity of 3 mmol g−1 for 1 vol% CO2 in N2 , along with

∼1 vol% H2

available bentonite for CO2

ceous materials for CO2

with ZnCl2

the ZnCl2

pathway in the frontier area of CO2

**2.4. Nanoporous carbon composite**

cal/chemical activation of carbonaceous materials with CO2

O at 60°C [72]. Xiao and coworkers exploited an inexpensive and commercially

immobilization of TEPA [73]. Hence, these low-cost clay based adsorbents introduce a new

procedure environmental friendly, robust, sustainable and thus a more attractive strategy.

Nanoporous carbon derived from various carbon precursors, such as polymer, biomass, coal, petroleum etc. shows enormous significance in small molecule adsorption due to high specific surface area, narrow pore size distribution, low preparation cost, easy-to-design, low energy requirements for regeneration, high stability in air and water and high flexibility in heteroatom doping/surface functionalization [74]. Porous carbons are prepared from physi-

are generally employed as activating agents for the formation of microporous carbon [75]. In addition, templating method using zeolites, ZSM-5, several MOFs (MOF-5, ZIF-8, Al-PCP)

Additionally, from the perspective of environmental friendliness and preparation cost, waste materials e.g. fly ash, coconut, carpet are quite popular to prepare high performance carbona-

hazelnut shells via carbonization and KOH activation. The obtained porous carbon exhibits a high specific surface area of ~1900 m<sup>2</sup> g−1 and high pore volume (1–0.7) cm3 g−1, which are approximately five times greater than those of carbon without activation [80]. Again, coffee residue has also been used as a sustainable source for the preparation of activated carbon

step carbonization from porous polymers. Recently, Modak et al. have prepared microporous carbon (K-COP-M) having extremely high surface area of 2186 m2 g−1 and contains micropore

**Figure 7.** Schematic presentation of the formation of porous carbon from MOFs, POPs, foam and waste materials.

[81]. The textural properties of the samples thus prepared significantly depend on

/C ratio. On the other hand, porous carbons are also prepared through a facile one

adsorption [77–79]. As for instance, porous carbons are prepared from

acts as an effective carbon precursors in making amorphous carbon (**Figure 7**) [76].

capture from flue gas after modified by sulfuric acid followed by

capture and sequestration study and should make the

Advances in Porous Adsorbents for CO2 Capture and Storage

http://dx.doi.org/10.5772/intechopen.70796

175

, steam, ZnCl2

, KOH etc., which

**Figure 6.** Schematic presentation of the trapping of CO2 from the seasonal ambient air in clay based solid nanocomposites, adapted from Ref. [11] with permission from The Royal Society of Chemistry.

∼1 vol% H2 O at 60°C [72]. Xiao and coworkers exploited an inexpensive and commercially available bentonite for CO2 capture from flue gas after modified by sulfuric acid followed by immobilization of TEPA [73]. Hence, these low-cost clay based adsorbents introduce a new pathway in the frontier area of CO2 capture and sequestration study and should make the procedure environmental friendly, robust, sustainable and thus a more attractive strategy.

#### **2.4. Nanoporous carbon composite**

and easily available HNTs to capture CO2

174 Carbon Dioxide Chemistry, Capture and Oil Recovery

et al. reported the adsorption of CO2

and at the excess sorption maximum. CO2

studied the kinetics of several stable isotopes of CO2

developed montmorillonite supported PEI composite for CO2

pores is comparatively stable over a wide range of CO2

spheric CO2

inorganic-organic CO2

from the ambient air under room temperature

onto kaolinite surfaces under geologic sequestration

sorption increases with decreasing temperature

present in the ambient air [68]. Schaef

capture [70]; the CO2

pressures at a given temperature

in N2

sorption

capture

in

and 10% CO2

capture efficiency

, along with

in the clay

and ambient pressure [67]. They have also explored the effect of relative humidity in terms of moisture on the adsorption kinetics of the adsorbents by carrying out the experiment on the seasonal ambient air [11], exhibiting that relative humidity basically regulates the atmo-

conditions and also verified through the density functional theory (DFT) [69]. Wang et al.

efficacy was found to be 2.54 mmol g−1 under dry environmental condition and 3.23 mmol g−1

while the high pressure sorption properties demonstrate weak temperature dependence.

through the modification of the surface of montmorillonite nanoclay using aminopropyl-

nitrogen gas streams the nanoclay loaded with only one of the amines exhibits ~6 wt% cap-

when the nanoclay immobilized with both the amines. Irani et al. utilized nanosepiolite as an

**Figure 6.** Schematic presentation of the trapping of CO2 from the seasonal ambient air in clay based solid nanocomposites,

adapted from Ref. [11] with permission from The Royal Society of Chemistry.

sorbent by immobilizing tetraethylenepentamine (TEPA) onto acid-

under moisture added condition. They also verified that the density of CO<sup>2</sup>

Elliot A. Roth and coworkers synthesized amine-containing solid sorbent for CO2

trimethoxysilane and polyethylenimine [71]. They found that in pure CO2

ture efficacy at 85°C and atmospheric pressure, whereas it is ~7.5 wt% CO<sup>2</sup>

modified nanosepiolite, having capacity of 3 mmol g−1 for 1 vol% CO2

adsorption and corresponding adsorption kinetics (**Figure 6**). Jana et al. also

Nanoporous carbon derived from various carbon precursors, such as polymer, biomass, coal, petroleum etc. shows enormous significance in small molecule adsorption due to high specific surface area, narrow pore size distribution, low preparation cost, easy-to-design, low energy requirements for regeneration, high stability in air and water and high flexibility in heteroatom doping/surface functionalization [74]. Porous carbons are prepared from physical/chemical activation of carbonaceous materials with CO2 , steam, ZnCl2 , KOH etc., which are generally employed as activating agents for the formation of microporous carbon [75]. In addition, templating method using zeolites, ZSM-5, several MOFs (MOF-5, ZIF-8, Al-PCP) acts as an effective carbon precursors in making amorphous carbon (**Figure 7**) [76].

Additionally, from the perspective of environmental friendliness and preparation cost, waste materials e.g. fly ash, coconut, carpet are quite popular to prepare high performance carbonaceous materials for CO2 adsorption [77–79]. As for instance, porous carbons are prepared from hazelnut shells via carbonization and KOH activation. The obtained porous carbon exhibits a high specific surface area of ~1900 m<sup>2</sup> g−1 and high pore volume (1–0.7) cm3 g−1, which are approximately five times greater than those of carbon without activation [80]. Again, coffee residue has also been used as a sustainable source for the preparation of activated carbon with ZnCl2 [81]. The textural properties of the samples thus prepared significantly depend on the ZnCl2 /C ratio. On the other hand, porous carbons are also prepared through a facile one step carbonization from porous polymers. Recently, Modak et al. have prepared microporous carbon (K-COP-M) having extremely high surface area of 2186 m2 g−1 and contains micropore

**Figure 7.** Schematic presentation of the formation of porous carbon from MOFs, POPs, foam and waste materials.

volume of 0.85 cm3 g−1 [82]. K-COP-M has been produced by KOH activation of COP-M polymer in an inert condition and at very high temperature (600–700°C). CO2 adsorption potential of K-COP-M-600/700 have been evaluated, indicating that these frameworks adsorb 160–170 cm3 g−1 (7.6–7.1 mmol g−1) CO2 at 1 atm and 273 K, which is higher than that of nonactivated carbon derived from COP-M (i.e. COP-M-600/700 stores 77–83 cm3 g−1 CO2 ). This signifies the utility of KOH in making effective adsorbents by creating ultra-small micropores in carbons. While heteroatom doping is significantly used in controlling the textural properties of porous carbon, carbonization of amine containing organic precursors substantially shows high N-doping and considers as an effective adsorbent of CO<sup>2</sup> with very good selectivity. There are several reports available in this respect [49, 83], among which N-doped composite developed by Kim et al. is interesting, where polyindole-reduced graphene oxide (PIG) hybrid was synthesized and later carbonized at 400–800°C temperature and thus produces N-doped graphene sheets [84]. The N-doped graphene sheets are microporous having 0.6 nm pores with BET surface area of about 936 m2 g−1 and show a maximum CO2 uptake of 3.0 mmol g−1 at 25°C and 1 atm pressure. Nevertheless, high recycling stability of CO2 uptake is noticed even after 10 recycling cycles; additionally this N-doped carbon shows CO2 /N2 , CO2 /CH4 separation ability of 23 and 4 respectively.

researchers to extend this work towards low pressure CO2

capture under ultra-dilute condition.

 and Subhra Jana1,2\* \*Address all correspondence to: subhra.jana@bose.res.in

world CO2

**Acknowledgements**

**Author details**

Arindam Modak1

**References**

Centre for Basic Sciences, Kolkata, India.

for Basic Sciences, Salt Lake, Kolkata, India

Geophysics. 2010;**48**:RG4004

2012;**112**:724-781

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ous amines. AICHE Journal. 2007;**53**:3144-3154

new route in the frontier area of carbon capture and sequestering study through the real

Authors would like to acknowledge Department of Science and Technology (DST), Government of India for funding (SR/NM/NS-18/2014 and SB/WEA-008/2016) and S. N. Bose National

1 Technical Research Centre, S. N. Bose National Centre for Basic Sciences, Salt Lake, Kolkata, India 2 Department of Chemical, Biological & Macro-Molecular Sciences, S. N. Bose National Centre

[1] Hansen J, Ruedy R, Sato M, Lo K. Global surface temperature change. Reviews of

[2] GISS Surface Temperature Analysis. Available from: http://data.giss.nasa.gov/gistemp/

[3] Pachauri RK, Meyer, L. A IPCC. Climate change 2014: Synthesis report. Contribution of Working Groups I, II and III to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change; Core Writing Team, editors. IPCC: Geneva, Switzerland, 2014.

[4] Reichle D, Houghton J, Kane B, Ekmann J. Carbon Sequestration. Washington, DC: State of the Science; U.S. Department of Energy, Office of Science, Office of Fossil Energy; 1999

[6] Wang W, Zhou M, Yuan D. Carbon dioxide capture in amorphous porous organic poly-

[7] Sumida K, Rogow DL, Mason JA, McDonald TM, Bloch ED, Herm ZR, Tae-Hyun Bae TH, Long JR. Carbon dioxide capture in metal-organic frameworks. Chemical Reviews.

[5] Oyenekan BA, Rochelle GT. Alternative stripper configurations for CO<sup>2</sup>

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adsorption, which may open a

177

http://dx.doi.org/10.5772/intechopen.70796

Advances in Porous Adsorbents for CO2 Capture and Storage

capture by aque-

Alternatively, polyurethane foams (PUFs) are important thermosetting polymers and owing to its high nitrogen contents, it can be used as good precursor for N-doped carbon [85]. The global demand for polyurethanes was estimated to be 13.6 million tons in 2010, which leads to the generation of huge wastes. However, regeneration of spent polyurethane is not only high energy-consuming process, but also it produces toxic nitrogen oxides, carbon oxides etc. and causing severe environmental pollution. These wastes when carbonized at high temperature can produce nitrogen-doped carbon that can further reduce environmental pollution since these N-doped carbon shows CO2 uptake capacities of 6.67 and 4.33 mmol g−1 at 0°C and 25°C under 1 bar, respectively. Finally, it can be said that like MOFs, POPs and porous clays, microporous carbon is also an alternative for CO2 storage purposes.
