4.8 Review

MOF-enabled confinement and related effects for chemical catalyst presentation and utilization

期刊

CHEMICAL SOCIETY REVIEWS
卷 51, 期 3, 页码 1045-1097

出版社

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1cs00968k

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资金

  1. DOE, Office of Science, Basic Energy Sciences [DE-SC0012702]
  2. U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences [DE-FG02-87ER13808, DE-FG02-08ER15967]
  3. Defense Threat Reduction Agency [HDTRA1-18-1-0003]
  4. National Science Foundation [DGE-1842165]
  5. U.S. DOE, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program
  6. DOE [DE-SC0014664]

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This review focuses on how porous, catalyst-containing MOFs utilize molecular-scale confinement to regulate reactant and product transport, catalyst activity, and stability, to achieve desired chemical transformations with superior selectivity or efficacy compared to catalysts in homogeneous solution environments.
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.

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