Electrosynthesis of Urea on High‐Density Ga─Y Dual‐Atom Catalyst via Cross‐Tuning
Dechao Chen, Yimeng Cai, Yi Xiao, Chengqiang Wang, Yong Li, Ke Ma, Dongdong Xiao, Hsiao‐Tsu Wang, Chi‐Feng Lee, Linjie Zhang, Hirofumi Ishii, Yu‐Cheng Shao, Nozomu Hiraoka, Lili Han, Xueming Liu, Huolin L. Xin
Abstract
Abstract Electrochemically converting carbon dioxide (CO 2 ) and nitrate (NO 3 − ) into urea via the C─N coupling route offers a sustainable alternative to the traditional industrial urea production technology, but it is still limited by poor yield rate, low Faradaic efficiency, and insufficient coupling kinetics. Herein, a high‐density Ga─Y dual‐atom catalyst is developed with loading up to 14.1 wt.% of Ga and Y supported on N, P‐co‐doped carbon substrate (Ga/Y‐CNP) for urea electrosynthesis. The catalyst facilitates efficient C─N coupling through co‐reduction of CO 2 and NO 3 − , resulting in a high urea yield rate of 41.9 mmol h −1 g −1 and a Faradaic efficiency of 22.1% at −1.4 V versus the reversible hydrogen electrode. In situ spectroscopy and theoretical calculations reveal that the superior performance is attributed to the cross‐tuning between adjacent pair Ga─Y sites, which can mutually optimize their electronic states for facilitating CO 2 reduction to *CO at Ga sites and promoting NO 3 − conversion to hydroxylamine (*NH 2 OH) at Y sites, followed by spontaneous coupling of *CO and *NH 2 OH intermediates at Ga─Y sites to form C─N bonds. This work offers a pioneering strategy to manipulate C─N coupling pathways by cross‐tuning active sites to produce high‐value‐added chemicals.