Elucidating Relay Catalysis on Copper Clusters With Satellite Single Atoms for Enhanced Urea Electrosynthesis
Xinyue Ma, Baoguang Mao, Zhong‐Zhen Yu, Dan Wang, Jing Xia, Jianhua Hou, Xiangmin Meng, Husitu Lin, Chuangang Hu
Abstract
Abstract Relay catalysis represents significant efficacy in alleviating competition among different reactants during coupling reactions. However, a comprehensive understanding of the reaction mechanism underlying relay catalysis for the urea electrosynthesis remains challenging. Herein, we have developed a catalyst (Cu AC ‐Cu SA @NC) comprising Cu atomic clusters (Cu AC ) with satellite Cu─N 4 single atoms (Cu SA ) sites on the nitrogen‐doped porous interconnected carbon skeleton (NC), enabling elucidation of a relay catalysis process for co‐reduction of CO 2 and NO 3 − . The designed Cu AC ‐Cu SA @NC catalyst exhibits an approximately threefold higher urea yield rate compared to that of Cu SA @NC at −1.3 V versus RHE. Ex‐situ experimental results and in‐situ attenuated total reflection surface‐enhanced infrared absorption spectroscopy analysis reveal a formation sequence between the *NH 2 and *NH 2 CO species on Cu AC ‐Cu SA @NC with increasing reduction potential. The combination of theoretical calculations further elucidates that the relay catalysis pathway involves “Cu AC ” sites facilitating the conversion of *NO 3 to *NO x , followed by a hydrogenation process to form *NH 2 with *H from water dissociation promoted by “Cu SA ” sites, which subsequently couples with *CO 2 to produce urea. This work provides novel insights into the investigation of coupling reactions, but not limit to, urea synthesis.