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Porous Chemical Architectures On lower figures, each of the corners is an oxygen-centered Zn4 tetrahedron bridged by six carboxylates of an organic linker. The large yellow spheres represent the largest sphere that would fit in the cavities without touching the van der Waals atoms of the frameworks. Hydrogen atoms have been omitted.9 Black, yellow, red, and green spheres represent C, B, O, and N atoms, respectively. Recently, new classes of molecularly designed crystalline porous solids have emerged as favorable candidates for gas separation and storage. These are MOFs, ZIFs, and covalent organic frameworks (COFs). MOFs are constructed from transition metal-oxide “joints” linked by organic “struts.” Typically, they are made in polar solutions by mixing a metal salt with an organic carboxylic acid to form insoluble crystalline solids of extended structures. ZIFs are a subclass of MOFs but have structures related to those of zeolites: the transition metal ions (Zn or Co) are bridged by an imidazolate-type link in the same way that the silicon atoms are bridged by an oxide in zeolites. Thus ZIFs are based on the tetrahedral structures of ZIFs. COFs are also crystalline porous solids, but they are entirely composed of light elements (H, B, C, O, N) and linked by strong covalent bonds into 3D porous architectures. MOFs, ZIFs, and COFs have expanded greatly the number of porous materials because of the flexibility with which their components can be varied and functionalized with organic units to make them suitable for gas separation applications. The advantage of using such porous chemical architectures for gas separations is the access to a large number of internal surface sites, as indicated by their high surface areas (zeolites, 500–900; silicas, ~1,000; porous carbon, 500–1,500; and MOFs, ZIFs, and COFs, 1,000–6,000 m2/g). The surface area is roughly proportional to the number of surface sites onto which gas molecules can bind, giving these materials very high capacity for storage of gases. The openness of the structures, especially the more recent ones, is immensely useful for fast kinetics in the uptake of gases and the removal of bound gases. 20PDF Image | 2020 Carbon Capture
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