Interlayer Spacing Regulation by Single‐Atom Indium<sup><i>δ</i>+</sup>–N<sub>4</sub> on Carbon Nitride for Boosting CO<sub>2</sub>/CO Photo‐Conversion
Cheng Ding, Xinxin Lu, Bo Tao, Liuqing Yang, Xiaoyong Xu, Lanqin Tang, Haoqiang Chi, Yong Yang, Debora Meira, Lu Wang, Xi Zhu, Si Li, Yong Zhou, Zhigang Zou
Abstract
Abstract Simultaneous optimization on bulk photogenerated‐carrier separation and surface atomic arrangement of catalyst is crucial for reactivity of CO 2 photo‐reduction. Rare studies capture the detail that, better than in‐plane regulation, interlayer‐spacing regulation may significantly influence the carrier transport of the bulk‐catalyst thereby affecting its CO 2 photo‐reduction in g ‐C 3 N 4 . Herein, through a single atom‐assisted thermal‐polymerization process, single‐atom In‐bonded N‐atom (In δ + –N 4 ) in the (002) crystal planes of g ‐C 3 N 4 is originally constructed. This In δ + –N 4 reduces the (002) interplanar spacing of g ‐C 3 N 4 by electrostatic adsorption, which significantly enhances the separation of bulk carriers and greatly promotes the reactivity of CO 2 photoreduction. The CO 2 photo‐conversion performance of this resulted single‐atom In modified g ‐C 3 N 4 is significantly superior to other single atom loaded carbon nitride catalysts. Moreover, the In δ + –N 4 enhances the CO 2 adsorption on g ‐C 3 N 4 , reduces the *COOH formation energy, and optimizes the reaction path. It achieves a remarkable 398.87 µmol g −1 h −1 yield rate, 0.21% apparent quantum efficiency, and nearly 100% selectivity for CO without any cocatalyst or sacrificial agent. Through d (002) modulation of carbon nitride by single In atom, this study provides a ground‐breaking insight for reactivity enhancement from a double‐gain view of bulk structural control and surface atomic arrangement for CO 2 ‐reduction photocatalysts.