Electronic Structure Manipulation <i>via</i> Site-Selective Atomically Dispersed Ni for Efficient Photocatalytic CO<sub>2</sub> Reduction
Yuyin Mao, Minghui Zhang, Shenghe Si, Guangyao Zhai, Xiaolei Bao, Kepeng Song, Lirong Zheng, Yuanyuan Liu, Zeyan Wang, Zhaoke Zheng, Peng Wang, Ying Dai, Hefeng Cheng, Baibiao Huang
Abstract
Single-atom catalysts (SACs) have recently emerged as promising photocatalysts for CO 2 reduction; however, understanding their interplay between the local electronic structure and the overall performance at an atomic level still remains elusive. Here, we construct two Ni-SACs at different sites of WO 2.72 nanowires, i.e., bulk doping of single Ni atoms in WO 2.72 (B-Ni 1 /WO 2.72 ) and surface anchoring of single Ni atoms on WO 2.72 (S-Ni 1 /WO 2.72 ), to unravel the electronic structure manipulation for boosting CO 2 photoreduction. Impressively, B-Ni 1 /WO 2.72 displays superior photocatalytic CO 2 reduction performance to S-Ni 1 /WO 2.72, reaching a CO yield of 80.5 mmol g –1 h –1 with a selectivity of 98.7%. Experimental results and computational calculations reveal that compared to S-Ni 1 /WO 2.72, B-Ni 1 /WO 2.72 is endowed with improved charge transfer and a more upshifted d -band center, thereby leading to CO production with concurrent high activity and selectivity. This work provides deeper insights into the exploration of efficient SACs for artificial photosynthesis to targeted products by optimization of their site-related electronic structures.