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 has been synthesized by using 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] units assembled into one crystalline structure according to a hydro(solvo)thermal method. This is a very rare case of a metal phosphite incorporating both N‐ and O‐donor ligands. The tetradentate TIMB linker bound to zinc atoms of the isolated zincophosphite hexamers to form a 3D open‐framework structure by crosslinking structural components of 1D chains and 2D layers. Here, the TPDC ligand acts as a monodentate binding model to functionalize its porous structure with the uncoordinated S atom and COO− group. Interestingly, this compound demonstrates the highest H2 storage capacity among organic–inorganic hybrid metal phosphates (and phosphites), and a good CO2 capture at 298 K compared with the majority of crystalline materials. The possible adsorption sites and selectivity for CO2 over H2, N2, and CO at 298 K were calculated by using density functional theory (DFT), the ideal adsorption solution theory (IAST), and fitting experimental pure‐component adsorption data. [ABSTRACT FROM AUTHOR]