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

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 di...

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Published in:Angewandte Chemie (International ed.) 2019-11, Vol.58 (46), p.16533-16537
Main Authors: 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.
Format: Article
Language:English
Subjects:
Active control
Bimetals
Catalysts
Crystal structure
Crystallinity
Density functional theory
DFT calculations
gas-phase reactions
heterogeneous catalysis
Hydrogen storage
Hydrogenation
Metal-organic frameworks
Metals
Nodes
Organic chemistry
Oxidation
Propylene
Rhodium
Room temperature
Valence
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Summary: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. 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. Selective catalytic hydrogenation of propylene to propane at room temperature occurs in the gas phase at the metal nodes of a crystalline CuRh bimetallic metal–organic framework. The RhII ions are identified as the catalytically active sites.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201908761