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Figure 20. A hierarchical membrane formed from molecular constituents via a self-directed assembly process. from nanostructures to hierarchical macroscopic constructs with self-assembly requires dynamic processes that trigger a sequence of physical events that build the structure. One might describe this process as pathway-dependent self-assembly, which is very likely to occur far from equilibrium. The example in Figure 20 shows molecules that assemble into a bilayer nanoscale membrane with two domains—one amorphous and one ordered—separating two liquids, leading to osmotic events that build, through diffusion, third and fourth layers with drastically different permeabilities. Permeability and mechanical behavior not only differ in the various compartments of this hierarchical membrane but also change as a function of time as the membrane grows further from simple reagents. One additional level of complexity in this type of membrane structure is its decoration with functional groups that can catalyze or react with molecules in specific compartments. The chemistry used in building this variety of hierarchical structures by self-assembly could combine both organic and inorganic chemistry to create new high-performance robust membranes. Creative work in this area of materials synthesis could easily integrate supramolecular nanostructures, covalent and supramolecular polymers, metal organic frameworks, and ceramic-like lattices. As we approach 2020, materials heterogeneous in both architecture and composition could offer surprising new ways to capture carbon. Materials chemistry. Membranes provide a powerful and generally enabling means to effect separations in complex fluid streams and have qualities that make them attractive for use in carbon capture. High transport rates and capacities for selectivity—combined with scalability and chemical, mechanical, and thermal stability in the process environment—are key attributes supporting their use. There remain significant challenges in developing next- generation membranes for carbon capture and storage, nonetheless. If highly scalable hierarchical structures are to contribute to next-generation membranes, advances in materials chemistry are required that will allow precise construction of these heterogeneous architectures. Multilayer laminates or surface textures offer additional degrees of freedom to tailor properties of hierarchical membranes. Polymer segmental motions and chemical interactions could be exploited to mediate solubility or diffusivity. Ceramic composition could be tailored to influence thermal expansion, vacancy concentrations, and so on. There is a significant need and opportunity to more fully develop the chemistry of membrane materials in ways that harness either chemical mechanisms or specific forms of interaction (e.g., facilitated transport) to influence permeation rates and selectivity. This work must deliver those capabilities within materials that are robust in application-specific conditions. Systems of interest include high-permeance materials that can catalyze specific, reversible CO2 transformations in ways that can then be hierarchically exploited in a low-energy separation. Materials are needed that can facilitate transport via specific but easily reversible 70PDF Image | 2020 Carbon Capture
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