A model catalyst for methanol synthesis: Zn-deposited and Zn-free Cu surfaces

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Abstract
The synthesis of methanol by the hydrogenation of CO2 over Zn‐deposited and Zn‐free single‐crystal coppersurfaces has been studied using an x‐ray photoelectron spectroscopy apparatus combined with a high‐pressure flow reactor (18 atm). The order of plane for the catalytic activity was (110)≳(311)≳(100)≳(111) for Zn‐free coppersurfaces. The Zn‐deposited Cu(111) (ΘZn=0.19) was 13 fold more active than the Zn‐free Cu(111). The activation energy for the methanol synthesis (73–84 kJ/mol) was close to each other regardless of the surface structure or the presence of Zn. It was shown that the Zn deposited on Cu(111) acted as a promoter for the methanol synthesis, while the Zn on Cu(110) and Cu(100) had no such a promotional effect. On the postreaction surfaces of Zn‐deposited and Zn‐free copper samples, a small amount of formate species was always detected which was more stable than that on clean Cusurfaces. This formate species’s coverage was proportional to the activity for methanol formation.

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