Cheng Lei, Yue Xiaoyang, Fan Jiajie, Xiang Quanjun
State Key Laboratory of Electronic Thin Film and Integrated Devices, School of Electronic Science and Engineering, University of Electronic Science and Technology of China, Chengdu, 610054, P. R. China.
Yangtze Delta Region Institute (Huzhou), University of Electronic Science and Technology of China, Huzhou, 313001, P. R. China.
Adv Mater. 2022 Jul;34(27):e2200929. doi: 10.1002/adma.202200929. Epub 2022 Jun 2.
Photoexcited dynamic modulation, maximizing the effective utilization of photoinduced electron-hole pairs, dominates the multiple electrons-involving reduction pathways for terminal CH evolution during CO 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 co-catalyst rather than carbon nitride supports, which can selectively favor CO -to-CH 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 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 formation. As a result, an unprecedented CH yield (181.7 µmol g ) is obtained with a high turnover number (411.4) through a fully gas-solid reaction, demonstrating its potential toward targeted CH formation without adding any sacrificial agent.
光激发动态调制最大化了光生电子-空穴对的有效利用，主导了CO光还原过程中涉及多个电子的终端CH演化的还原途径。然而，通过修饰S型异质结来实现定向电荷转移的位点特异性调控却鲜有讨论。在此，报道了一种原子级剪裁策略，即将单原子Co锚定到CeO助催化剂而非氮化碳载体上，这能够选择性地促进CO到CH的光还原。通过原位动态跟踪研究，该研究确定表面嵌入Co的双金属CeCo结合是通过S型异质结驱动动态电荷状态强互连的关键特征。将Co嵌入CeO助催化剂被证明对定向电荷控制具有关键作用，加速了电子从氮化碳供体向位点特异性Co中心的驱动，从而促进了涉及电子的CH形成的电子转移能力。结果，通过完全的气-固反应获得了前所未有的CH产率（181.7 µmol g）和高周转数（411.4），证明了其在不添加任何牺牲剂的情况下实现靶向CH形成的潜力。
