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Hydrogenation Of CO2 To Methanol On CeOx/Cu(111) And ZnO/Cu(111) Catalysts: Role Of The Metal–Oxide Interface And Importance Of Ce3+ Sites

S. Senanayake, P. Ramírez, I. Waluyo, S. Kundu, K. Mudiyanselage, Zongyuan Liu, Z. Liu, S. Axnanda, D. Stacchiola, J. Evans, J. Rodriguez
Published 2016 · Chemistry

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The role of the interface between a metal and oxide (CeOx–Cu and ZnO–Cu) is critical to the production of methanol through the hydrogenation of CO2 (CO2 + 3H2 → CH3OH + H2O). The deposition of nanoparticles of CeOx or ZnO on Cu(111), θoxi < 0.3 monolayer, produces highly active catalysts for methanol synthesis. The catalytic activity of these systems increases in the sequence: Cu(111) < ZnO/Cu(111) < CeOx/Cu(111). The apparent activation energy for the CO2 → CH3OH conversion decreases from 25 kcal/mol on Cu(111) to 16 kcal/mol on ZnO/Cu(111) and 13 kcal/mol on CeOx/Cu(111). The surface chemistry of the highly active CeOx–Cu(111) interface was investigated using ambient pressure X-ray photoemission spectroscopy (AP-XPS) and infrared reflection absorption spectroscopy (AP-IRRAS). Both techniques point to the formation of formates (HCOO–) and carboxylates (CO2δ−) during the reaction. Our results show an active state of the catalyst rich in Ce3+ sites which stabilize a CO2δ− species that is an essential inter...
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