We have investigated coprecipitated Cu-based catalysts possessing different metal oxide additives, Cu crystallite sizes, and varying degrees of support crystallinity. Using a variety of ex situ and in situ characterization techniques, we have verified that Cu0 species are active sites for methanol synthesis from a stoichiometric CO2/H2 mixture. The possibility of Cu+ species acting as active sites is excluded because these species are not observed on the surface of the working catalysts. The reaction is structure-sensitive with smaller Cu particles demonstrating higher turnover frequency. An explanation for an activity enhancement upon promotion will be presented. Possible reaction pathways for CO2 hydrogenation to methanol will also be discussed.
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