Abstract Cu/ZrO2 is a promising catalyst for the hydrogenation of CO2 to methanol. Reaction pathways involving formates or hydroxycarbonyls have been proposed. We show here that three different types of formates can be observed under reaction conditions at 220 °C and 3 bar, one being located on metallic Cu and two others being bound to ZrO2. The surface concentrations of formates were determined through calibration curves and their reactivity measured during chemical transient experiments. The Cu‐bound formate represented only about 7 of surface formates, but exhibited a higher reactivity and was found to be the only formate that could account for all the production of methanol. Copper is thus not there only to activate H2, but also bears other crucial intermediates. This work reemphasizes that fully quantitative IR analyses and transient methods are required to unravel the role of surface species.
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