Abstract
A defining characteristic of nearly all catalytically functional MOFs is uniform, molecular-scale porosity. MOF pores, linkers and nodes that define them, help regulate reactant and product transport, catalyst siting, catalyst accessibility, catalyst stability, catalyst activity, co-catalyst proximity, composition of the chemical environment at and beyond the catalytic active site, chemical intermediate and transition-state conformations, thermodynamic affinity of molecular guests for MOF interior sites, framework charge and density of charge-compensating ions, pore hydrophobicity/hydrophilicity, pore and channel rigidity vs. flexibility, and other features and properties. Collectively and individually, these properties help define overall catalyst functional behaviour. This review focuses on how porous, catalyst-containing MOFs capitalize on molecular-scale confinement, containment, isolation, environment modulation, energy delivery, and mobility to accomplish desired chemical transformations with potentially superior selectivity or other efficacy, especially in comparison to catalysts in homogeneous solution environments.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 1045-1097 |
| Number of pages | 53 |
| Journal | Chemical Society Reviews |
| Volume | 51 |
| Issue number | 3 |
| DOIs | |
| State | Published - Feb 7 2022 |
Funding
For support of our own work in the field of gas-phase MOF catalysis, we acknowledge the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Science, Basic Energy Sciences (DE-SC0012702). For work on photochemical and electrochemical catalysis we acknowledge U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (grant DE-FG02-87ER13808). For work relevant to reactive separations we acknowledge the U.S. Department of Energy, Office of Science, Basic Energy Sciences (grant DE-FG02-08ER15967). For work on catalytic destruction of chemical threats, we acknowledge support from the Defense Threat Reduction Agency (HDTRA1-18-1-0003). Z. H. S., M. C. W., and J. G. K. acknowledge support from the National Science Foundation Graduate Research Fellowship program under Grant No. (DGE-1842165). T. A. G. gratefully acknowledges the support of the U.S. DOE, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE, and ORISE is managed by ORAU under Contract DE-SC0014664.
ASJC Scopus subject areas
- General Chemistry