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Genuine Pores in a Stable Zinc Phosphite for High H2 Adsorption and CO2 Capture.

An uncommon example of stable mixed-ligand zinc phosphite with genuine pores was synthesized by zinc metal, inorganic phosphite acid, thio-functionalized O-donor (2,5-thiophenedicarboxylate, TPDC), and tetradentate N-donor [1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene, TIMB] building units assembled into one crystalline structure grown by hydro(solvo)thermal method. This is a very rare case of metal phosphite incorporating both N- and O-donor ligands. The tetradentate TIMB linker bond to zinc atoms of the isolated zincophosphite hexamers to form a 3D open-framework structure by cross-linking of structural components of 1D chains and 2D layers. Here, the TPDC ligand acts as a monodentate binding modal to functionalize its porous structure with the uncoordinated S atom and COO - group. Remarkably, this compound demonstrates the highest H 2 storage capacity among organic-inorganic hybrid metal phosphates (and phosphites) and an excellent CO 2 capture at 298 K compared with the majority of crystalline materials. The possible adsorption sites and selectivity for CO 2 over H 2 , N 2 , and CO at 298 K were calculated using density functional theory (DFT), the ideal adsorption solution theory (IAST), and fitting experimental pure-component adsorption data.