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Title: Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks

Journal Article · · Angewandte Chemie
 [1];  [1];  [2];  [3];  [1];  [1];  [1];  [4];  [5];  [3];  [6];  [6];  [2];  [1]; ORCiD logo [1]
  1. Department of Chemistry and Biochemistry University of South Carolina Columbia SC 29208 USA
  2. Department of Chemistry University of Tennessee Knoxville TN 37996 USA
  3. Chemistry Division Brookhaven National Laboratory Upton NY 11973 USA
  4. Department of Materials Science and Chemical Engineering Stony Brook University Stony Brook NY 11794 USA
  5. Chemistry Division Brookhaven National Laboratory Upton NY 11973 USA, Department of Materials Science and Chemical Engineering Stony Brook University Stony Brook NY 11794 USA
  6. Department of Chemical Engineering University of South Carolina Columbia SC 29208 USA

Abstract We report the first study of a gas‐phase reaction catalyzed by highly dispersed sites at the metal nodes of a crystalline metal–organic framework (MOF). Specifically, CuRhBTC (BTC 3− =benzenetricarboxylate) exhibited hydrogenation activity, while other isostructural monometallic and bimetallic MOFs did not. Our multi‐technique characterization identifies the oxidation state of Rh in CuRhBTC as +2, which is a Rh oxidation state that has not previously been observed for crystalline MOF metal nodes. These Rh 2+ sites are active for the catalytic hydrogenation of propylene to propane at room temperature, and the MOF structure stabilizes the Rh 2+ oxidation state under reaction conditions. Density functional theory calculations suggest a mechanism in which hydrogen dissociation and propylene adsorption occur at the Rh 2+ sites. The ability to tailor the geometry and ensemble size of the metal nodes in MOFs allows for unprecedented control of the active sites and could lead to significant advances in rational catalyst design.

Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0019360
OSTI ID:
1573065
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 131 Journal Issue: 46; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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