Engineering Active Sites of Gold-Cuprous Oxide Catalysts for Electrocatalytic Oxygen Reduction Reaction

Understanding how the catalyst morphology influences surface sites is crucial for designing active and stable catalysts and electrocatalysts. We here report a new approach to this understanding by decorating gold (Au) nanoparticles on the surface of cuprous oxides (Cu₂O) with three different shape morphologies (spheres, cubes, and petals). The Au-Cu₂O particles are dispersed onto carbon nanotube (CNT) matrix with high surface area, stability, and conductivity for oxygen reduction reaction. A clear morphology-dependent enhancement of the electrocatalytic activity is revealed. Oxygenated gold species (AuO^-) are found to coexist with Au⁰ on the cube and petal catalysts, whereas only Au⁰ species are present on the sphere catalyst. The AuO^- species function effectively as active sites, resulting in the improved catalytic performance by changing the reaction mechanism. The enhanced catalytic performance of the petal-shaped catalyst in terms of onset potential, half-wave potential, diffusion-limited current density, and stability is closely associated with the presence of the most abundant AuO^- species on its surface. Highly active AuO^- species are identified on the surface of the catalysts as a result of the unique structural characteristics, which is attributed to the structural origin of high activity and stability. This insight constitutes the basis for assessing the detailed correlation between the morphology and the electrocatalytic properties of the nanocomposite catalysts, which has implications for the design of surface-active sites on metal/metal oxide electrocatalysts.