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Most solid porous sorbent materials have 3D architectures (see the sidebar “Porous Chemical Architectures”) that increase the surface area available for sorption and thereby increase the capacity of the material. To ensure facile kinetics for uptake and release of CO2, solid sorbents can be designed to have very large surface-to-volume ratios. Most such materials are made up of porous solids or high- surface-area particulates, such as activated carbon,1 zeolites, and other porous silica-based materials.2 The primary mode of CO2 uptake is physisorption, resulting from interactions between the gas and the material. The current limitations of these types of solid adsorbents for gas sorption include low capacity of CO2 uptake in porous carbons and the energy required for removal of CO2 from zeolites. There is enormous potential for making solid materials highly selective for the adsorption of targeted gases by modifying the surfaces with specific materials or functional groups.3 For example, activated carbon materials can be enriched with elements that could result in improved properties. This includes substituting nitrogen for some carbon atoms or impregnating the material with metal ions. These “extra-framework” atoms and metal ions can serve as specific sites for selective adsorption of CO2.4 Further, when the interior pores of activated carbons, zeolites, or mesoporous silicates are functionalized with amines, they can reversibly form surface-tethered carbamates upon exposure to induce chemisorption and increase the uptake efficiency at low partial pressures of CO2.5–7 A similar approach can be applied to the surfaces of small solid particles, providing a high-surface-area amine- functionalized solid support. While these initial studies with surface modifications show considerable promise, a molecular understanding of the interaction of targeted gases with these functional groups is critically needed to design new sorbents with higher selectivity. This knowledge will also help explain the role of moisture content in the uptake and release efficiency as these new materials are used in real applications.8 One can imagine developing solid sorbents that would incorporate functionalities that mimic the mechanism nature uses to isolate CO2 from air. Such mechanisms are found in conversion of CO2 to sugars in plant photosynthesis and expulsion of CO2 in respiration in animals. Further, it may also be possible to incorporate active materials into solid sorbents that could introduce entirely new modes of capturing and releasing CO2. For example, it might be feasible to introduce functionalities that can respond to magnetic fields or radio frequency radiation to facilitate concentration/release of the CO2. Incorporating a material that exhibits a phase transformation near the temperature of separation could allow the exothermic energy of CO2 uptake to be adsorbed and later recovered to aid in CO2 release. Recently, a new class of materials has been discovered that have considerable potential as solid sorbents, including metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) (see “Porous Chemical Architectures”). These novel crystals and network Figure 3. The adsorbent material can be designed to be highly size- and shape- selective. 19PDF Image | 2020 Carbon Capture
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