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

Abstract Here it is shown that polyoxometalate (POM) clusters (H 3 PW 12 O 40 · x H 2 O, PW 12 ) 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 PW 12 clusters), which continue to grow into copolymer‐analogue Au−PW 12 sub‐1 nm nanowires. Due to the synergetic effect of Au nanoclusters and POMs, the obtained Au−PW 12 sub‐1 nm nanowires efficiently perform catalytic activity in the photo‐electrochemical converting CO 2 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 CO 2 reduction reaction.