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

Abstract

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 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. 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.

Authors:
 [1];  [1];  [2]; ORCiD logo [3];  [1];  [1];  [1];  [4];  [5];  [3];  [1];  [1];  [2];  [1]; ORCiD logo [1]
  1. Univ. of South Carolina, Columbia, SC (United States)
  2. Univ. of Tennessee, Knoxville, TN (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Stony Brook Univ., NY (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1569548
Alternate Identifier(s):
OSTI ID: 1573065
Report Number(s):
BNL-212166-2019-JAAM
Journal ID: ISSN 0044-8249
Grant/Contract Number:  
SC0012704; SC0019360; SC0012335
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Name: Angewandte Chemie; Journal ID: ISSN 0044-8249
Publisher:
German Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DFT-Rechnungen; Gasphasenreaktionen; Heterogene Katalyse; Metall-organische Gerüste; Rhodium

Citation Formats

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., and Chen, Donna A. Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks. United States: N. p., 2019. Web. doi:10.1002/ange.201908761.
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. Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks. United States. doi:10.1002/ange.201908761.
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., and Chen, Donna A. Tue . "Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks". United States. doi:10.1002/ange.201908761.
@article{osti_1569548,
title = {Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks},
author = {Shakya, Deependra M. and Ejegbavwo, Otega A. and Rajeshkumar, Thayalan and Senanayake, Sanjaya D. and Brandt, Amy J. and Farzandh, Sharfa and Acharya, Narayan and Ebrahim, Amani M. and Frenkel, Anatoly I. and Rui, Ning and Tate, Gregory L. and Monnier, John R. and Vogiatzis, Konstantinos D. and Shustova, Natalia B. and Chen, Donna A.},
abstractNote = {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 (BTC3-=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.},
doi = {10.1002/ange.201908761},
journal = {Angewandte Chemie},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {9}
}

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