Open AccessAlternative Pathway of CO2 Hydrogenation by Lewis-Pair-Functionalized UiO-66 MOF Revealed by Metadynamics Simulations
Author(s) -
Mojgan Heshmat
Publication year - 2020
Publication title -
journal of physical chemistry. c./journal of physical chemistry. c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.401
H-Index - 289
eISSN - 1932-7455
pISSN - 1932-7447
DOI - 10.1021/acs.jpcc.0c01088
Subject(s) - metadynamics , lewis acids and bases , intramolecular force , density functional theory , chemistry , computational chemistry , frustrated lewis pair , catalysis , covalent bond , materials science , molecular dynamics , stereochemistry , organic chemistry
The reaction between H 2 and CO 2 catalyzed by an intramolecular frustrated Lewis pair, which is covalently bonded to a UiO-66 metal-organic framework (MOF), is considered in this work. Free energy surfaces (FESs) for this reaction are generated throughout finite-temperature density functional theory (DFT) metadynamics (MD) simulations. The simulated FESs indicate an alternative stepwise pathway for the hydrogenation of CO 2 . Furthermore, indications of weaker binding of CO 2 than H 2 to the Lewis pair centers have been observed via metadynamics simulations. These findings were unknown from the results of static-DFT calculations, which proposed a concerted reduction of CO 2 . The results of the present work may influence the design of new efficient heterogeneous Lewis pair (LP)-functionalized MOFs to catalyze capture and conversion of CO 2 to high-value chemicals.