Atomically Dispersed ZnN<sub>4</sub> Sites Anchored on P‐Functionalized Carbon with Hierarchically Ordered Porous Structures for Boosted Electroreduction of CO<sub>2</sub>
Chenghong Hu, Wen Yao, Xianfeng Yang, Kui Shen, Liyu Chen, Yingwei Li
Abstract
Abstract Tuning the coordination structures of metal sites is intensively studied to improve the performances of single‐atom site catalysts (SASC). However, the pore structure of SASC, which is highly related to the accessibility of active sites, has received little attention. In this work, single‐atom ZnN 4 sites embedded in P‐functionalized carbon with hollow‐wall and 3D ordered macroporous structure (denoted as H‐3DOM‐ZnN 4 /P‐C) are constructed. The creation of hollow walls in ordered macroporous structures can largely increase the external surface area to expose more active sites. The introduction of adjacent P atoms can optimize the electronic structure of ZnN 4 sites through long‐rang regulation to enhance the intrinsic activity and selectivity. In the electrochemical CO 2 reduction reaction, H‐3DOM‐ZnN 4 /P‐C exhibits high CO Faradaic efficiency over 90% in a wide potential window (500 mV) and a large turnover frequency up to 7.8 × 10 4 h −1 at −1.0 V versus reversible hydrogen electrode, much higher than its counterparts without the hierarchically ordered structure or P‐functionalization.