Electrochemical Carbon Dioxide Reduction Reaction or Hydrogen Evolution Reaction: Kernel and Type-Dependent Catalytic Activity of Staples in Metal Nanoclusters

Abstract

Due to the challenge of finding adequate structures for the catalytic activity assessment of various staples in metal nanoclusters, a fast-oxidation method is introduced to obtain a kinetics-controlled metal nanocluster Au₂₄(CHT)₁₈ with modified structure of the previously reported Au₂₄(SR)₂₀ (SR: thiolate). It is found that the staple catalysis activity is affected by the kernel, transforming the catalysis selectivity from H₂ evolution to CO production [H₂ Faradaic efficiency: ≈100% for Au₂₄(SR)₂₀ at −0.8 V versus CO Faradaic efficiency: 91% for Au₂₄(SR)₁₈], and the staple catalysis activity order is tetramer > monomer > dimer, which is further confirmed by comparing the catalysis performance between Au₂₄(CHT)₁₈ and Au₁₈(CHT)₁₄. Thus, the kernel influence on the staple catalysis and the staple activity order in catalysis is revealed, and with essential implications provided for metal nanocluster synthesis, structure tailoring, and structure–property correlation. The additional photoluminescence endows the as-prepared nanoclusters potential for more practical applications.