Many efforts have been made to model adsorption and diffusion processes in metalorganic frameworks (MOFs) in the past several years. In most of these studies, the framework has been kept rigid. In this study, we examine the effect of using a flexible framework model on the self-diffusion coefficients and activation energies calculated for several short n-alkanes and benzene in IRMOF-1 from mole...

Defects and inclusions in metal-organic frameworks (MOFs) have captured the attention of the scientific community as a possible new source of interesting functionalities. Currently, little is known about how the presence of defects and guest molecules affects adsorptive, catalytic, mechanical and other properties of a MOF crystal and there is a clear need for a comprehensive theoretical framewo...

Density Functional Theory (DFT) calculations techniques in terms of energetic and electronics properties are used to study CO2 adsorption in NH2-, OH-, COOH-, Br- and Cl-functionalized IRMOF-1. Geometry optimization, density of states (DOS), and energy analyses were performed to investigate the adsorption phenomenon. First, we examined the geometrical as well as the electronic structures of fun...

Hydrogen spillover on carbon-based systems has been proposed as a viable alternative for room-temperature storage. Given the strength of the C-H bonds, however, it is unclear if spillover indeed takes place in such materials. We performed a first-principles study of H spillover on IRMOF-1. Spillover becomes thermodynamically stable only at high H coverage with a calculated Gibbs free energy of ...

A series of unprecedented crown ether- and thiacrown ether-derivatized benzene dicarboxylic acid (H2bdc) ligands has been synthesized and incorporated into the prototypical isoreticular metal-organic framework (IRMOF) and UiO-66 materials. In the case of UiO-66, only MOFs comprised from a mixed-ligand composition, requiring both unsubstituted bdc and crown ether containing ligands, could be pre...

Formic acid production from CO2 allows the reduction of carbon dioxide emissions while synthesizing a product with wide range applications. hydrogenation is challenging due to cost transition metal catalysts and toxicity elements. In this work, thermodynamic confinement effects metal–organic framework UiO-66 on formic were studied by force field-based molecular simulations. The frameworks Cu-BT...

We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal–organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We fi nd that the hybrid B3LYP (Becke three-parameter Lee–Yang–Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular link...

Isoreticular metal organic frameworks (IRMOFs) have shown high uptake capabilities for storage of H₂ (11.5 wt % at 77 K and 170 bar). A significant literature has employed fragment models and a single adsorbed H₂ to identify adsorption sites within IRMOFs, as well as the necessary adsorbate-adsorbent interactions needed to reach sufficient adsorption enthalpy for practical usage, however at hig...