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 (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.
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1569548
- Alternate Identifier(s):
- OSTI ID: 1573299
- 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 Volume: 131; Journal Issue: 46; Journal ID: ISSN 0044-8249
- Publisher:
- German Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
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/anie.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. https://doi.org/10.1002/anie.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. https://doi.org/10.1002/anie.201908761. https://www.osti.gov/servlets/purl/1569548.
@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/anie.201908761},
journal = {Angewandte Chemie},
number = 46,
volume = 131,
place = {United States},
year = {Tue Sep 17 00:00:00 EDT 2019},
month = {Tue Sep 17 00:00:00 EDT 2019}
}
Web of Science
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