Rhodium single-atom catalyst design through oxide support modulation for selective gas-phase ethylene hydroformylation

Farpón, Marcos G. ; Henao, Wilson ; Plessow, Philipp N. ; Andrés, Eva ; Arenal, Raúl ; Marini, Carlo ; Agostini, Giovanni ; Studt, Félix ; Prieto, Gonzalo

Resumen: A frontier challenge in single-atom (SA) catalysis is the design of fully inorganic sites capable of emulating the high reaction selectivity traditionally exclusive of organometallic counterparts in homogeneous catalysis. Modulating the direct coordination environment in SA sites, via the exploitation of the oxide support's surface chemistry, stands as a powerful albeit underexplored strategy. We report that isolated Rh atoms stabilized on oxygen-defective SnO2 uniquely unite excellent TOF with essentially full selectivity in the gas-phase hydroformylation of ethylene, inhibiting the thermodynamically favored olefin hydrogenation. Density Functional Theory calculations and surface characterization suggest that substantial depletion of the catalyst surface in lattice oxygen, energetically facile on SnO2, is key to unlock a high coordination pliability at the mononuclear Rh centers, leading to an exceptional performance which is on par with that of molecular catalysts in liquid media.

Idioma: Inglés

DOI: 10.1002/anie.202214048

Año: 2023

Publicado en: Angewandte Chemie (International ed.) 62, 1 (2023), e202214048 [9 pp.]
ISSN: 1433-7851

Factor impacto JCR: 16.1 (2023)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 14 / 231 = 0.061 (2023) - Q1 - T1

Factor impacto CITESCORE: 26.6 - Chemistry (all) (Q1) - Catalysis (Q1)

Factor impacto SCIMAGO: 5.3 - Chemistry (miscellaneous) (Q1) - Catalysis (Q1)

Financiación: info:eu-repo/grantAgreement/ES/AEI/PRE2019-087571
Financiación: info:eu-repo/grantAgreement/ES/DGA/E13-20R
Financiación: info:eu-repo/grantAgreement/EC/ERC/2019/CoG/864195
Financiación: info:eu-repo/grantAgreement/EC/H2020/823717/EU/Enabling Science and Technology through European Electron Microscopy/ESTEEM3
Financiación: info:eu-repo/grantAgreement/ES/MICINN-AEI/PID2019-104739GB-I00/AEI-10.13039-501100011033
Financiación: info:eu-repo/grantAgreement/ES/MICINN/FPU17-04701
Financiación: info:eu-repo/grantAgreement/ES/MICINN/FPU17-04751
Financiación: info:eu-repo/grantAgreement/ES/MICINN/RTI2018-096399-A-I00

Tipo y forma: Article (Published version)