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COOPERATIVE PHENOMENA FOR LOW NET ENTHALPY OF CYCLING Abstract Cooperative processes are those that can be accomplished by coupling the binding of a target gas with a change in a structure or other change in the sorbent material to lower the overall energy cost of the coupled uptake and release process. Taking advantage of cooperative phenomena has the potential to greatly enhance the thermal efficiency of gas sorption processes. To discover and exploit these cooperative phenomena, computational tools will be required to guide the discovery and design of a new generation of separation materials. Background and Motivation This PRD seeks to enhance the efficiency of reversible gas sorption by developing new materials systems that exploit the coupling of gas sorption with the underlying molecular structure of materials. The thesis of this concept is that the thermal efficiency of gas sorption (CO2, in this case) can be significantly enhanced by coupling the gas binding process with a structural (or chemical) change in the material to which the gas binds so as to enhance thermal efficiency. In noncooperative binding, each sorbent-CO2 binding interaction is thermodynamically downhill (exothermic); therefore, an energy cost is associated with subsequent release of the CO2 from the sorbent, which adds to the overall cost of CO2 capture and release. If the binding of CO2 can be intimately coupled with another process that requires (endothermic) energy (e.g., a structural change in a molecule), the overall energy required for release of CO2 will be diminished. The coupling of CO2 binding with a change in the properties of the sorbent is what we mean by cooperative phenomena. This idea is inspired by examples in nature, for example, the reversible binding of oxygen to hemoglobin. This area of research has the potential to substantially lower the cost of CO2 (or other gas) capture and release by reducing the parasitic heat cost of CO2 release and by decreasing the price of oxygen production for oxycombustion and precombustion processes. The types of changes that might occur in the sorbent material span a wide range of length scales, from the molecular to the macroscopic; and, indeed, different types of materials will exhibit changes at different length scales. Gas binding can, for example, induce subtle structural changes at the molecular scale in transition metal coordination compounds. On the other hand, the volume of highly porous materials can change by macroscopic amounts upon uptake of molecular species; an example is water incorporation into a sponge. Building on this concept, changes in the sorbent material that would lead to either uptake or release of gases could also be triggered by external stimuli, such as an applied voltage, or mechanical stresses that have a low energy cost compared with heating (see the PRD “Alternative Driving Forces and Stimuli-Responsive Materials for Carbon Capture”). Achieving this concept will require the discovery, synthesis, and assembly of new materials systems, along with characterization and modeling of these novel processes. Investigation of various materials that respond to the binding of CO2, O2, or other gases will provide fundamental information that will yield insight into how best to exploit this approach. It is possible that changes on a specific length scale will be optimal for achieving the goal of low net enthalpy for the overall process. 63PDF Image | 2020 Carbon Capture
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