Tailoring surface morphology on anatase TiO2 supported Au nanoclusters: implications for O2 activation

Strong interaction between the support surface and metal clusters activates the adsorbed molecules at the metal cluster-support interface. Using plane-wave DFT calculations, we precisely model the interface between anatase TiO2 and small Au nanoclusters. Our study focusses on the adsorption and activation of oxygen molecules on anatase TiO2, considering the influence of oxygen vacancies and steps on the surface. We find that the plane (101) and the stepped (103) surfaces do not support O-2 activation, but the presence of oxygen vacancies results in strong adsorption and O-O bond length elongation. Modifying the TiO2 surface with supported small Aun nanoclusters (n = 3-5) also significantly enhances O-2 adsorption and stretches the O-O bond. We observe that manipulating the cluster orientation through discrete rotations results in improved O-2 adsorption and promotes charge transfer from the surface to the molecule. We propose that the orientation of the supported cluster may be manipulated by making the cluster adsorb at the step-edge of (103) TiO2. This results in activated O-2 at the cluster-support interface, with a peroxide-range bond length and a low barrier for dissociation. Our modeling demonstrates a straightforward means of exploiting the interface morphology for O-2 activation under low precious metal loading, which has important implications for electrocatalytic oxidation reactions and the rational design of supported catalysts.