Clusters induced electronic delocalization of single atom sites toward efficient electrocatalytic urea synthesis from CO2 and N2

Zhi-Hao Zhao; Ruyi Jiang; Hexu Niu; Meng Wang; Jingnan Wang; Yu Du; Yajie Tian; Menglei Yuan; Guangjin Zhang; Zongjing Lu

doi:10.1016/j.jcis.2024.11.217

Clusters induced electronic delocalization of single atom sites toward efficient electrocatalytic urea synthesis from CO₂ and N₂

J Colloid Interface Sci. 2024 Nov 28:682:222-231. doi: 10.1016/j.jcis.2024.11.217. Online ahead of print.

Authors

Zhi-Hao Zhao¹, Ruyi Jiang², Hexu Niu², Meng Wang³, Jingnan Wang⁴, Yu Du⁵, Yajie Tian⁶, Menglei Yuan⁷, Guangjin Zhang⁸, Zongjing Lu⁹

Affiliations

¹ State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an 710072, China.
² Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology and Department of Advanced Chemical Engineering, School of Chemistry and Chemical Engineering, Queen Mary University of London Engineering School, Northwestern Polytechnical University, 710129 Xi'an, China.
³ School of Materials Engineering, Xi'an Aeronautical University, Xi'an 710077, China.
⁴ Institute of Molecular Plus, Tianjin University, Tianjin 300072, China.
⁵ SINOPEC Research Institute of Safety Engineering Co., Ltd, State Key Laboratory of Chemical Safety, Qingdao 266104, China.
⁶ School of Energy Science and Technology, Henan University, Zhengzhou, 450046, China.
⁷ State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an 710072, China. Electronic address: mlyuan@nwpu.edu.cn.
⁸ CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China. Electronic address: zhanggj@ipe.ac.cn.
⁹ Institute of Photochemistry and Photofunctional Materials, University of Shanghai for Science and Technology, Shanghai 200093, China. Electronic address: zongjinglu@usst.edu.cn.

PMID: 39616652
DOI: 10.1016/j.jcis.2024.11.217

Abstract

Electrocatalytic conversion of CO₂ and N₂ into urea product is highly envisaged, whereas symmetrical electronic architecture of inert reactant severely prevents their adsorption and activation and further entail extremely low intrinsic activity. Herein, a novel electrocatalyst consisting of Co clusters and CoN₃ single-atoms dispersed on a carbon matrix is demonstrated to achieve the highest recorded urea yield rate of 20.83 mmol h^-1 g^-1 and Faradaic efficiency (FE) of 23.73 % at -0.4 V vs. RHE. Detailed investigations reveal that the concerted interplay between Co atomic clusters (Co_AC) and plane-asymmetric Co-N₃ single atom sites in CoN₃-Co_AC/NC specimen readily induced the unique electron delocalization effects and further prompted the orbital spin state of Co sites evolved from 3d⁷4s¹ to 3d⁸4s⁰, which optimized the adsorption configuration of the reactants, polarized the gas molecules through interaction with the bonding and antibonding orbitals of the optimized catalysts and eventually lowered the CN coupling barriers to produce the desired urea product.

Keywords: C-N coupling; Electronic delocalization; N(2) and CO(2) co-reaction; Spin state regulation; Urea electrosynthesis.