Phosphine-induced conversion from Au₃₆ to Au₃₂ for constructing a high-performance CO₂RR catalyst

Taking Au₃₆(CHT)₂₄ (Au₃₆ for short) as a precursor, a Au₃₂(CHT)₂₀(TFP) (Au₃₂ for short) nanocluster is obtained with the aid of a phosphine-mediated approach. Structural analysis shows that Au₃₂ is obtained by modifying and transforming the surface structure of the parent Au₃₆ nanocluster, including the removal of a surface layer of the core structure and the rearrangement of the surface motifs. Most importantly, this structural transformation results in a change in the position of some of the surface motifs, thus exposing the active domain with bare core metal atoms. The electrocatalytic CO₂ reduction reaction is introduced to investigate the effect of the modification of the surface structure on its properties. The results show that the modified structure of Au₃₂ exhibits superior catalytic activity with a faradaic efficiency (for CO) of 97.7% at -0.8 V.