Site‐Specific Electron‐Driving Observations of CO<sub>2</sub>‐to‐CH<sub>4</sub> Photoreduction on Co‐Doped CeO<sub>2</sub>/Crystalline Carbon Nitride S‐Scheme Heterojunctions
Lei Cheng, Xiaoyang Yue, Jiajie Fan, Quanjun Xiang
Abstract
Abstract Photoexcited dynamic modulation, maximizing the effective utilization of photoinduced electron–hole pairs, dominates the multiple electrons‐involving reduction pathways for terminal CH 4 evolution during CO 2 photoreduction. Yet, the site‐specific regulation of directional charge transfer by modification of an S‐scheme heterojunction has seldom been discussed. Herein, an atomic‐level tailoring strategy by anchoring single‐atomic Co into CeO 2 co‐catalyst rather than carbon nitride supports, which can selectively favor CO 2 ‐to‐CH 4 photoreduction, is reported. Through in situ dynamic tracking investigations, this study identifies that surface Co‐embedded bimetallic CeCo conjunction is the key feature driving a strong interconnection of dynamical charge states through S‐scheme heterojunctions. The Co‐embedded modification into CeO 2 co‐catalysts is demonstrated to have a critical effect on directional charge control, accelerating the driving of electrons from the carbon nitride donations to site‐specific Co hubs, which thereby promotes electronic transferability for electrons‐involving CH 4 formation. As a result, an unprecedented CH 4 yield (181.7 µmol g −1 ) is obtained with a high turnover number (411.4) through a fully gas–solid reaction, demonstrating its potential toward targeted CH 4 formation without adding any sacrificial agent.