Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks

Mandal, Mukunda; Cramer, Christopher J.; Truhlar, Donald G.; Sauer, Joachim; Gagliardi, Laura

doi:10.1021/acscatal.0c02300

Title: Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks

Journal Article · Thu Aug 06 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c02300· OSTI ID:1721719

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Univ. of Minnesota, Minneapolis, MN (United States)
Humboldt-Univ. zu Berlin (Germany)

Single-site catalysts with active species anchored over metal–organic framework (MOF) supports have garnered significant interest in recent years. Catalysts with vanadium oxide (VO_x) species immobilized over Zr-NU-1000 and Hf-MOF-808 (which have nodes containing six Zr^(IV) or Hf^(IV) ions, respectively) were recently characterized experimentally and were reported to be active for the selective oxidation of benzyl alcohol to benzaldehyde. Here, we report a detailed computational investigation of these VO_x-incorporated MOF catalysts (V-MOF) by employing density functional theory. Based on the mode of VO_x attachment, various structures are explored, and their relative stabilities and computed IR spectral features are reported. Mechanisms for the selective oxidation reaction are investigated. The analysis of electron flow in the turnover-limiting C–H activation step shows that the hydrogen-atom abstraction process involves a concerted proton-coupled electron-transfer mechanism. Here, the results of this study suggest that in addition to the identity of the metal in the node, the MOF node architecture plays a crucial role in driving the catalytic activities of V-MOFs.

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Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012702

OSTI ID:: 1721719

Journal Information:: ACS Catalysis, Vol. 10, Issue 17; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT modeling
metal−organic framework
single-site catalyst
vanadium
proton-coupled electron transfer
alcohols
metal organic frameworks
chemical structure
catalysts
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Title: Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks

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