Surface overgrowth on gold nanoparticles modulating high-energy facets for efficient electrochemical CO₂ reduction

Electrochemical CO₂ reduction reaction (eCO₂RR) has been considered one of the potential technologies to store electricity from renewable energy sources into chemical energy. For this aim, designing catalysts with high surface activities is critical for effective eCO₂RR. In this study, we introduced a surface overgrowth method on stable Au icosahedrons to generate Au nanostars with large bumps. As a catalyst for eCO₂RR, the Au nanostars exhibited a maximum faradaic efficiency (FE) of 98% and a mass activity of 138.9 A g^-1 for CO production, where the latter was one of the highest activities among Au catalysts. Despite the deducted electrochemically active surface area per mass, the high-energy surfaces from overgrowth provided a 3.8-fold larger specific activity than the original Au icosahedral seeds, resulting in superior eCO₂RR performances that outweigh the trade-off of size and shape in nanoparticles. The Au nanostars also represented prolonged stability due to the durability of high-energy facets. The characterization of surface morphology and density functional theory calculations revealed that predominant Au(321) facets on the Au nanostars effectively stabilized *COOH adsorbates, thus lowering the overpotential and improving the FE for CO production. This overgrowth method is simple and universal for various materials, which would be able to extend into a wide range of electrochemical catalysts.