Electroreduction of CO₂ on Au(310)@Cu High‐index Facets

The chemical selectivity and faradaic efficiency of high‐index Cu facets for the CO₂ reduction reaction (CO₂RR) is investigated. More specifically, shape‐controlled nanoparticles enclosed by Cu {hk0} facets are fabricated using Cu multilayer deposition at three distinct layer thicknesses on the surface facets of Au truncated ditetragonal nanoprisms (Au DTPs). Au DTPs are shapes enclosed by 12 high‐index {310} facets. Facet angle analysis confirms DTP geometry. Elemental mapping analysis shows Cu surface layers are uniformly distributed on the Au {310} facets of the DTPs. The 7 nm Au@Cu DTPs high‐index {hk0} facets exhibit a CH₄ : CO product ratio of almost 10 : 1 compared to a 1 : 1 ratio for the reference 7 nm Au@Cu nanoparticles (NPs). Operando Fourier transform infrared spectroscopy spectra disclose reactive adsorbed *CO as the main intermediate, whereas CO stripping experiments reveal the high‐index facets enhance the *CO formation followed by rapid desorption or hydrogenation.