Controlling the Size of Au Nanoparticles on Reducible Oxides with the Electrochemical Potential

Controlling the size of Au nanoparticles (NPs) and their interaction with the oxide support is important for their catalytic performance in chemical reactions, such as CO oxidation and water-gas shift. It is known that the oxygen vacancies at the surface of support oxides form strong chemical bonding with the Au NPs and inhibit their coarsening and deactivation. The resulting Au/oxygen vacancy interface also acts as an active site for oxidation reactions. Hence, small Au NPs are needed to increase the density of the Au/oxide interface. A dynamic way to control the size of the Au NPs on an oxide support is desirable but has been missing in the field. Here, we demonstrate an electrochemical method to control the size of the Au NPs by controlling the surface oxygen vacancy concentration of the support oxide. Oxides with different reducibilities, La_0.8Ca_0.2MnO_3±δ and Pr_0.1Ce_0.9O_2-δ, are used as model support oxides. By applying the electrochemical potential, we achieve a wide range of effective oxygen pressures, pO₂ (10^-37-10¹⁴ atm), in the support oxides. Applying the cathodic potential creates a high concentration of oxygen vacancies and forms finely distributed Au NPs with sizes of 7-13 nm at 700-770 °C in 10 min, while the anodic potential oxidizes the surface and increases the size of the Au NPs. The onset cathodic potential required to create small Au NPs depends strongly on the reducibility of the support oxide. The Au NPs did not undergo sintering even at 700-770 °C under the cathodic potential and also were stable in catalytically relevant conditions without potential.