| Sumario: | A detailed understanding of the interactions among the active components in gallium promoted Cu/ZnO catalysts, depending on the speciation of the gallium, are reported using in situ/operando spectroscopic studies, and their effect in the CO hydrogenation to methanol unraveled. In this contribution, the promoting effect of Ga-doped in the wurtzite ZnO lattice of a Cu/ZnO/GaO catalyst is compared to that of a zinc gallate (ZnGaO) phase. Remarkably, a strong inhibition of CO formation, together with an enhanced methanol formation, are observed in the Ga-doped ZnO sample, specifically at conditions where the competitive reverse water gas shift reaction predominates. The catalytic performance has been correlated with the microstructure of the catalyst where a surface enrichment with reduced ZnO species, together with the stabilization of positive charged copper species and an increase in the amount of surface basic sites for CO adsorption are observed on the most selective sample.
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