A Cu/ZnO/Al2O3 commercial catalyst for methanol synthesis from syngas was investigated under operational conditions. HERFD XAS and EXAFS data were recorded under different reaction gas mixtures, temperatures, and pressures. Activation of the catalyst precursor occurred via a Cu+ intermediate. The active catalyst predominantly consists of metallic Cu and ZnO. Methanol production only starts when all accessible Cu is reduced. The structure of the active catalyst did not change with temperature or pressure even though the methanol yield changed strongly. Formation of a carbon-containing layer on top of the catalyst surface was detected by TPD, which was correlated with a several-hour induction period in the methanol production after the catalyst reduction.
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