Electronic Structure Manipulation via Site-Selective Atomically Dispersed Ni for Efficient Photocatalytic CO₂ Reduction

Single-atom catalysts (SACs) have recently emerged aspromisingphotocatalysts for CO2 reduction; however, understandingtheir interplay between the local electronic structure and the overallperformance at an atomic level still remains elusive. Here, we constructtwo Ni-SACs at different sites of WO2.72 nanowires, i.e., bulk doping of single Ni atoms in WO2.72 (B-Ni-1/WO2.72) and surface anchoring of singleNi atoms on WO2.72 (S-Ni-1/WO2.72),to unravel the electronic structure manipulation for boosting CO2 photoreduction. Impressively, B-Ni-1/WO2.72 displays superior photocatalytic CO2 reduction performanceto S-Ni-1/WO2.72, reaching a CO yield of 80.5mmol g(-1) h(-1) with a selectivityof 98.7%. Experimental results and computational calculations revealthat compared to S-Ni-1/WO2.72, B-Ni-1/WO2.72 is endowed with improved charge transfer and amore upshifted d-band center, thereby leading toCO production with concurrent high activity and selectivity. Thiswork provides deeper insights into the exploration of efficient SACsfor artificial photosynthesis to targeted products by optimizationof their site-related electronic structures.