Au‐Polyoxometalates A‐B‐A‐B Type Copolymer‐Analogue Sub‐1 nm Nanowires

Abstract

Here it is shown that polyoxometalate (POM) clusters (H₃ PW₁₂ O₄₀ ·xH₂ O, PW₁₂ ) can be introduced to interact with Au nanoclusters to form the "A-B-A-B" type building block ("A" represents Au nanoclusters and "B" stands for PW₁₂ clusters), which continue to grow into copolymer-analogue Au-PW₁₂ sub-1 nm nanowires. Due to the synergetic effect of Au nanoclusters and POMs, the obtained Au-PW₁₂ sub-1 nm nanowires efficiently perform catalytic activity in the photo-electrochemical converting CO₂ into CO. Under light, the catalyst maintains remarkable faradic efficiency (FE) of ≈99% from -0.7 to -0.9V (RHE), which is better than that in dark (FE of 66.4-90.64% from -0.7 to -0.9 V (RHE)). Density functional theory calculations and cryo-electron microscope images support the "A-B-A-B" type of structure and mechanistic studies also reveal the higher reactivity toward COOH* formation and CO adsorption on the catalyst, which lead to the superior catalytic activity in CO₂ reduction reaction.