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

Shakya, Deependra M.; Ejegbavwo, Otega A.; Rajeshkumar, Thayalan; Senanayake, Sanjaya D.; Brandt, Amy J.; Farzandh, Sharfa; Acharya, Narayan; Ebrahim, Amani M.; Frenkel, Anatoly I.; Rui, Ning; Tate, Gregory L.; Monnier, John R.; Vogiatzis, Konstantinos D.; Shustova, Natalia B.; Chen, Donna A.

doi:10.1002/anie.201908761

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

Journal Article · 17 September 2019 · Angewandte Chemie

DOI: https://doi.org/10.1002/anie.201908761 · OSTI ID:1569548

Shakya, Deependra M. ^[1]; Ejegbavwo, Otega A. ^[1]; Rajeshkumar, Thayalan ^[2];

^[3]; Brandt, Amy J. ^[1]; Farzandh, Sharfa ^[1]; Acharya, Narayan ^[1]; Ebrahim, Amani M. ^[4]; Frenkel, Anatoly I. ^[5]; Rui, Ning ^[3]; Tate, Gregory L. ^[1]; Monnier, John R. ^[1]; Vogiatzis, Konstantinos D. ^[2]; Shustova, Natalia B. ^[1];

^[1]

Univ. of South Carolina, Columbia, SC (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Stony Brook Univ., NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)

In this paper, 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 Rh²⁺ sites are active for the catalytic hydrogenation of propylene to propane at room temperature, and the MOF structure stabilizes the Rh²⁺ oxidation state under reaction conditions. Density functional theory calculations suggest a mechanism in which hydrogen dissociation and propylene adsorption occur at the Rh²⁺ sites. Laslty, 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.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC0012704; SC0019360; SC0012335

OSTI ID:: 1569548

Alternate ID(s):: OSTI ID: 1573299

Report Number(s):: BNL-212166-2019-JAAM

Journal Information:: Angewandte Chemie, Vol. 131, Issue 46; ISSN 0044-8249

Publisher:: German Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 22 works

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References (23)

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