Moderate Intermediate Adsorption Boosts Electrocatalytic C─N Coupling via Coordination Engineering
Abstract
ABSTRACT The electrocatalytic synthesis of urea from carbon dioxide and nitrate represents a sustainable route, with the C─N coupling between *CO and *NO intermediates being critical. However, achieving high efficiency remains challenging due to insufficient control over intermediate adsorption and reaction pathways. In this work, we reveal that the coordination number (CN) of Cu inversely regulates the adsorption strength of *CO and *NO, while C─N coupling activity follows a volcano‐type relationship with CN. Alloying Cu with intrinsically inert Ga atoms lowers the CN of Cu, upshifts d ‐band center, and finely tunes intermediate adsorption, thereby facilitating the formation of the key *ONCO. The optimized Cu 0.875 Ga 0.115 catalyst, with a moderate CN of 9.3 situated between its counterparts (6.0 and 12.0), balances adsorption and coupling activity, delivering a desirable urea yield rate of 575.6 mmol h −1 g −1 and a Faradaic efficiency of 30.4% at −1.4 V versus RHE. This work underscores coordination engineering as an effective strategy for guiding efficient C─N coupling toward urea synthesis.
Article Details
Authors (17)
Kefan Zhang
State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education
Peilian Hou
State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education
Yuyan Liu
Xupeng Qin
National Synchrotron Radiation Laboratory
Chu Zhang
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Space Power-Sources, School of Chemistry and Chemical Engineering
Mingming Wang
Department of Applied Chemistry, School of Chemistry and Materials Science, Hefei National Research Center for Physical Sciences at the Microscale
Chade Lv
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Space Power-Sources, School of Chemistry and Chemical Engineering
Dafeng Yan
Hubei Key Laboratory for Precision Synthesis of Small Molecule Pharmaceuticals & Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, College of Chemistry and Chemical Engineering
Dawei Chen
State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education
Ze Wu
Yujie Wang
Shenyang National Laboratory for Materials Science, Institute of Metal Research
Han Xu
Wenqi Gao
State Key Laboratory of Chemo and Biosensing College of Chemistry and Chemical Engineering International Joint Lab of Energy Electrochemistry of the Ministry of Education Hunan University Changsha China
Xinyu Zhou
Qinghua Liu
National Synchrotron Radiation Laboratory
Shuangyin Wang
State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering
Chen Chen