An oxidized magnetic Au single atom on doped TiO2(110) becomes a high performance CO oxidation catalyst due to the charge effect

Catalysis using gold nanoparticles supported on oxides has been under extensive investigation for many important application processes. However, how to tune the charge state of a given Au species to perform a specific chemical reaction, e.g. CO oxidation, remains elusive. Here, using first-principles calculations, we show clearly that an intrinsically inert Au anion deposited on oxygen-deficient TiO2(110) (Au@TiO2(110)) can be tuned and optimized into a highly effective single atom catalyst (SAC), due to the depletion of the d-orbital by substrate doping. Particularly, Ni- and Cu-doped Au@TiO2 complexes undergo a reconstruction driven by one of the two dissociated O atoms upon CO oxidation. The remaining O atom heals the surface oxygen vacancy and results in a stable bow-shaped surface O-Au-O species; thereby the highly oxidized Au single atom now exhibits magnetism and dramatically enhanced activity and stability for O-2 activation and CO oxidation, due to the emergence of high density of states near the Fermi level. Based on further extensive calculations, we establish the charge selection rule for O-2 activation and CO oxidation on Au: the positively charged Au SAC is more active than its negatively charged counterpart for O-2 activation, and the more positively charged the Au, the more active it is.