Inert Heteroatom Substitution to Modulate Dual‐Metal‐Sites for Boosting Photoreduction of Diluted CO<sub>2</sub>
Yibo Dou, Congjia Luo, Boyu Yin, Awu Zhou, Jibo Qin, Chang Ming Li, Wenjing Zhang, Dingsheng Wang, Jian‐Rong Li
Abstract
Abstract The precise regulation of active sites to steer reaction pathway for photocatalytic CO 2 reduction is critical, but remains challenges. Herein, an inert heteroatom substitution strategy is developed to activate adjacent dual‐active‐sites for boosting photocatalytic reduction of diluted CO 2 . As a proof of concept, Co 2+ δ /Ni 2+ ζ dual‐active‐sites in layered double hydroxides (LDHs) photocatalyst with high activity is interspaced and regulated by inert Al substitution. The corresponding elementary reaction step is optimized, where the Ni 2+ ζ site shows high activation of CO 2 reduction and weak absorption of *CO, whilst the Co 2+ δ site facilitates water oxidation. Most importantly, the produced *H on the Co 2+ δ site is synchronized with the formation of *COOH on the Ni 2+ ζ site, which synergistically lowers the energy barrier (*CO 2 to *COOH) of the rate‐determining step. Resulting CoNiAl‐LDHs photocatalyst attains nearly 100% selectivity with a production rate of 784 µmol g −1 h −1 toward diluted CO 2 reduction to CO, representing the best performance reported to date. This work delivers a feasible strategy via inert site substitution to activate proximate dual sites, which provides fundamental guidance to design photocatalysts for CO 2 reduction.