Light-Assisted Catalysis and the Dynamic Nature of Surface Species in the Reverse Water Gas Shift Reaction over Cu/γ-Al 2 O 3 .

Autor: Lorber K; National Institute of Chemistry, Hajdrihova 19, Ljubljana SI-1000, Slovenia.; University of Nova Gorica, Vipavska 13, Nova Gorica SI-5000, Slovenia., Arčon I; University of Nova Gorica, Vipavska 13, Nova Gorica SI-5000, Slovenia.; Jožef Stefan Institute, Jamova Cesta 39, Ljubljana SI-1000, Slovenia., Huš M; National Institute of Chemistry, Hajdrihova 19, Ljubljana SI-1000, Slovenia.; Association for Technical Culture of Slovenia, Zaloška 65, Ljubljana SI-1000, Slovenia.; Institute for the Protection of Cultural Heritage, Poljanska 40, Ljubljana SI-1000, Slovenia., Zavašnik J; Jožef Stefan Institute, Jamova Cesta 39, Ljubljana SI-1000, Slovenia., Sancho-Parramon J; Ruđer Bošković Institute, Bijenička Cesta 54, Zagreb 10000, Croatia., Prašnikar A; National Institute of Chemistry, Hajdrihova 19, Ljubljana SI-1000, Slovenia., Likozar B; National Institute of Chemistry, Hajdrihova 19, Ljubljana SI-1000, Slovenia., Novak Tušar N; National Institute of Chemistry, Hajdrihova 19, Ljubljana SI-1000, Slovenia.; University of Nova Gorica, Vipavska 13, Nova Gorica SI-5000, Slovenia., Djinović P; National Institute of Chemistry, Hajdrihova 19, Ljubljana SI-1000, Slovenia.; University of Nova Gorica, Vipavska 13, Nova Gorica SI-5000, Slovenia.
Jazyk: angličtina
Zdroj: ACS applied materials & interfaces [ACS Appl Mater Interfaces] 2024 Dec 11; Vol. 16 (49), pp. 67778-67790. Date of Electronic Publication: 2024 Nov 28.
DOI: 10.1021/acsami.4c15849
Abstrakt: The reverse water gas shift (RWGS) reaction converts CO 2 and H 2 into CO and water. We investigated Cu/γ-Al 2 O 3 catalysts in both thermally driven and light-assisted RWGS reactions using visible light. When driven by combined visible light and thermal energy, the CO 2 conversion rates were lower than in the dark. Light-assisted reactions showed an increase in the apparent activation energy from 68 to 87 kJ/mol, indicating that light disrupts the energetically favorable pathway active in the dark. A linear correlation between irradiance and decreasing reaction rate suggests a photon-driven phenomenon. In situ diffuse reflectance infrared Fourier transform spectroscopy and TD-DFT analyses revealed that catalyst illumination causes significant, partly irreversible surface dehydroxylation, highlighting the importance of OH groups in the most favorable RWGS pathway. This study offers a novel approach to manipulate surface species and control activity in the RWGS reaction.
Databáze: MEDLINE