Light-assisted catalysis and the dynamic nature of surface species in the reverse water gas shift reaction over ▫$Cu/\gamma-Al_2O_3$▫Lorber, Kristijan (Avtor) Arčon, Iztok (Avtor) Huš, Matej (Avtor) Zavašnik, Janez (Avtor) Sancho-Parramon, Jordi (Avtor) Prašnikar, Anže (Avtor) Likozar, Blaž (Avtor) Novak Tušar, Nataša (Avtor) Djinović, Petar (Avtor) The reverse water gas shift (RWGS) reaction converts CO2 and H2 into CO and water. We investigated Cu/γ-Al2O3 catalysts in both thermally driven and light-assisted RWGS reactions using visible light. When driven by combined visible light and thermal energy, the CO2 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.American Chemical Society20242024-12-19 09:10:00Neznano21079ACS applied materials & interfacessl© 2024 The Authors. Published by American Chemical Society