title: Rational Design of a Low-Cost, High-Performance Metal-Organic Framework for Hydrogen Storage and Carbon Capture.
abstract: We present thein silicodesign of a MOF-74 analogue, hereon known as M2(DHFUMA) [M = Mg, Fe, Co, Ni, Zn], with enhanced small-molecule adsorption properties over the original M2(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 M2(DHFUMA) framework has a reduced channel diameter, resulting in higher volumetric density of open metal sites and significantly improved volumetric hydrogen (H2) storage potential. Furthermore, the reduced distance between two adjacent open metal sites in the pore channel leads to a CO2binding 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 CO2:H2O mixtures, we theoretically predict the M2(DHFUMA) series as an improved alternative for carbon capture over the M2(DOBDC) series when adsorbing from wet flue gas streams. The improved CO2uptake 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 CO2capture and H2storage. The dynamical and elastic stabilities of Mg2(DHFUMA) were verified by hybrid DFT calculations, demonstrating its significant potential for experimental synthesis.
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California , Berkeley 94720, California, United States.
authors.forename: Matthew
authors.initials: M
authors.lastname: Witman
authors.affiliation: Department of Chemistry, University College London , 20 Gordon Street, London WC1H 0AJ, U.K.
authors.forename: Sanliang
authors.initials: S
authors.lastname: Ling
authors.affiliation: Laboratory of Molecular Simulation, Institut des Sciences et Ingénierie Chimiques, Valais, Ecole Polytechnique Fédérale de Lausanne (EPFL) , Rue de l' Industrie 17, CH-1951 Sion, Switzerland.
authors.forename: Andrzej
authors.initials: A
authors.lastname: Gladysiak
authors.affiliation: Laboratory of Molecular Simulation, Institut des Sciences et Ingénierie Chimiques, Valais, Ecole Polytechnique Fédérale de Lausanne (EPFL) , Rue de l' Industrie 17, CH-1951 Sion, Switzerland.
authors.forename: Kyriakos C
authors.initials: KC
authors.lastname: Stylianou
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley 94720, California, United States; Laboratory of Molecular Simulation, Institut des Sciences et Ingénierie Chimiques, Valais, Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l' Industrie 17, CH-1951 Sion, Switzerland.
authors.forename: Berend
authors.initials: B
authors.lastname: Smit
authors.affiliation: Department of Chemistry, University College London , 20 Gordon Street, London WC1H 0AJ, U.K.
authors.forename: Ben
authors.initials: B
authors.lastname: Slater
authors.affiliation: Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States; IMDEA Materials Institute, C/Eric Kandel 2, 28906 Getafe, Madrid, Spain.
authors.forename: Maciej
authors.initials: M
authors.lastname: Haranczyk