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In₂O₃ 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 In₂O₃ 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 In₂O₃ but also for other reducible oxide catalysts.

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