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Commercial P25 modified by Au-Cu alloy nanoparticles as thin film exhibits, for CO2 reduction by water under sun simulated light, a rate of methane production above 2000 μmol (g of photocatalyst)(-1) h(-1). Although evolution of hydrogen is observed and O2 and ethane detected, the selectivity of conduction band electrons for methane formation is almost complete, about 97%. This photocatalytic behavior is completely different from that measured for Au/P25 (hydrogen evolution) and Cu/P25 (lower activity, but similar methane selectivity). Characterization by TEM, XPS, and UV-vis spectroscopy shows that Au and Cu are alloyed in the nanoparticles. FT-IR spectroscopy and chemical analysis have allowed one to detect on the photocatalyst surface the presence of CO2(•-), Cu-CO, and elemental C. Accordingly, a mechanism in which the role of Au is to respond under visible light and Cu binds to CO and directs the reduction pathway is proposed.
Neațu et al. (2014) studied this question.