Flame Synthesis of Cu/ZnO–CeO(2) Catalysts: Synergistic Metal–Support Interactions Promote CH(3)OH Selectivity in CO(2) Hydrogenation

[Image: see text] The hydrogenation of CO(2) to CH(3)OH is an important reaction for future renewable energy scenarios. Herein, we compare Cu/ZnO, Cu/CeO(2), and Cu/ZnO–CeO(2) catalysts prepared by flame spray pyrolysis. The Cu loading and support composition were varied to understand the role of Cu–ZnO and Cu–CeO(2) interactions. CeO(2) addition improves Cu dispersion with respect to ZnO, owing to stronger Cu–CeO(2) interactions. The ternary Cu/ZnO–CeO(2) catalysts displayed a substantially higher CH(3)OH selectivity than binary Cu/CeO(2) and Cu/ZnO catalysts. The high CH(3)OH selectivity in comparison with a commercial Cu–ZnO catalyst is also confirmed for Cu/ZnO–CeO(2) catalyst prepared with high Cu loading (∼40 wt %). In situ IR spectroscopy was used to probe metal–support interactions in the reduced catalysts and to gain insight into CO(2) hydrogenation over the Cu–Zn–Ce oxide catalysts. The higher CH(3)OH selectivity can be explained by synergistic Cu–CeO(2) and Cu–ZnO interactions. Cu–ZnO interactions promote CO(2) hydrogenation to CH(3)OH by Zn-decorated Cu active sites. Cu–CeO(2) interactions inhibit the reverse water–gas shift reaction due to a high formate coverage of Cu and a high rate of hydrogenation of the CO intermediate to CH(3)OH. These insights emphasize the potential of fine-tuning metal–support interactions to develop improved Cu-based catalysts for CO(2) hydrogenation to CH(3)OH.