In2 O3 has emerged as a promising catalyst for CO2 activation, but a fundamental understanding of its mode of operation in CO2 hydrogenation is still missing, as the application of operando vibrational spectroscopy is challenging due to absorption effects. In this mechanistic study, we systematically address the redox processes related to the reverse water-gas shift reaction (rWGSR) over In2 O3 nanoparticles, both at the surface and in the bulk. Based on temperature-dependent operando UV/Vis spectra and a novel operando impedance approach for thermal powder catalysts, we propose oxidation by CO2 as the rate-determining step for the rWGSR. The results are consistent with redox processes, whereby hydrogen-containing surface species are shown to exhibit a promoting effect. Our findings demonstrate that oxygen/hydrogen dynamics, in addition to surface processes, are important for the activity, which is expected to be of relevance not only for In2 O3 but also for other reducible oxide catalysts.
Keywords: CO2 Activation; In2O3; Operando Spectroscopy; Reaction Mechanism; Reverse Water-Gas Shift.
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.