Rational Design of a Low-Cost, High-Performance Metal–Organic Framework for Hydrogen Storage and Carbon Capture

[Image: see text] We present the in silico design of a MOF-74 analogue, hereon known as M(2)(DHFUMA) [M = Mg, Fe, Co, Ni, Zn], with enhanced small-molecule adsorption properties over the original M(2)(DOBDC) series. Constructed from 2,3-dihydroxyfumarate (DHFUMA), an aliphatic ligand which is smaller than the aromatic 2,5-dioxidobenzene-1,4-dicarboxylate (DOBDC), the M(2)(DHFUMA) framework has a reduced channel diameter, resulting in higher volumetric density of open metal sites and significantly improved volumetric hydrogen (H(2)) storage potential. Furthermore, the reduced distance between two adjacent open metal sites in the pore channel leads to a CO(2) binding mode of one molecule per two adjacent metals with markedly stronger binding energetics. Through dispersion-corrected density functional theory (DFT) calculations of guest–framework interactions and classical simulation of the adsorption behavior of binary CO(2):H(2)O mixtures, we theoretically predict the M(2)(DHFUMA) series as an improved alternative for carbon capture over the M(2)(DOBDC) series when adsorbing from wet flue gas streams. The improved CO(2) uptake and humidity tolerance in our simulations is tunable based upon metal selection and adsorption temperature which, combined with the significantly reduced ligand expense, elevates this material’s potential for CO(2) capture and H(2) storage. The dynamical and elastic stabilities of Mg(2)(DHFUMA) were verified by hybrid DFT calculations, demonstrating its significant potential for experimental synthesis.