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closed nonporous state to an open porous state upon gas binding. Note that this phase change is gas-specific, occurring only in the presence of O2 and not of other gases, including Ar and N2, suggesting that such systems could be appropriately tuned for selective CO2 or O2 capture. Inspiration for new smart separation materials could perhaps be taken from nature. Biological cells take advantage of alternative driving forces such as pH gradients across membranes to drive protein and small molecule transport. Separation processes that use light-driven ion transport have been proposed,5 as shown in Figure 25 in which a spiropyran-crown ether conjugate molecule enhances the diffusion of potassium ions across a membrane. Upon photoisomerization of the molecule to the less stable, more polar form, the molecule more easily travels to the ion-rich interface at which an ion is coordinated (i.e., captured) by the molecule. Then the molecule, which is coordinated with the ion, travels across the membrane and releases the ion at the other interface. Upon release of the ion, the molecule reverts to its original form, allowing the process to repeat. These examples provide exciting inspiration for identifying new driving forces for gas separations that can be harnessed with novel materials to reduce or remove the need for energy-intensive approaches to concentrating CO2 from combustion streams, O2 from air for oxycombustion, and other applications. Figure 25. Scheme for light-driven transmembrane transport. Photoisomerization (1) converts the carrier molecule to a more mobile form that then relocates to the ion-rich interface (2), where the molecule binds with an ion (3), and travels across the membrane (4). The ion is then released at the opposite interface (5) before the carrier molecule returns to its original state (6), allowing the process to repeat. Source: R. F. Khairutdinov and J. K. Hurst, “Light-driven transmembrane ion transport by spiropyran−crown ether supramolecular assemblies,” Langmuir 20(5), 1781–1785 (2004). Inspiration for smart materials can also be garnered from other fields of materials chemistry, such as controlled drug delivery. For example, light-driven molecular impellers have been2 designed within silicon mesopores to increase the pressure and flow of a fluid (Figure 26). Stimulation by light causes the impellers to “wag,” thereby releasing the contents of the pores. Related systems have employed removable molecular caps on the exteriors of silica mesopores.6 The general design principles of such smart materials might be considered for selective gas sorption and transport. 79PDF Image | 2020 Carbon Capture
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