Probing active sites for carbon oxides hydrogenation on Cu/TiO using infrared spectroscopy.

The valorization of carbon oxides on metal/metal oxide catalysts has been extensively investigated because of its ecological and economical relevance. However, the ambiguity surrounding the active sites in such catalysts hampers their rational development. Here, in situ infrared spectroscopy in combination with isotope labeling revealed that CO molecules adsorbed on Ti and Cu interfacial sites in Cu/TiO gave two disparate carbonyl peaks. Monitoring each of these peaks under various conditions enabled tracking the adsorption of CO, CO, H and HO molecules on the surface. At room temperature, CO was initially adsorbed on the oxygen vacancies to produce a high frequency CO peak, Ti-CO. Competitive adsorption of water molecules on the oxygen vacancies eventually promoted CO migration to copper sites to produce a low-frequency CO peak. In comparison, the presence of gaseous CO inhibits such migration by competitive adsorption on the copper sites. At temperatures necessary to drive CO and CO hydrogenation reactions, oxygen vacancies can still bind CO molecules, and H spilled-over from copper also competed for adsorption on such sites. Our spectroscopic observations demonstrate the existence of bifunctional active sites in which the metal sites catalyze CO dissociation whereas oxygen vacancies bind and activate CO molecules.