A Universal Approach for Sustainable Urea Synthesis via Intermediate Assembly at the Electrode/Electrolyte Interface

Xiaojin Tu; Xiaorong Zhu; Shuowen Bo; Xiaoran Zhang; Ruping Miao; Guobin Wen; Chen Chen; Jing Li; Yangyang Zhou; Qinghua Liu; Dawei Chen; Huaiyu Shao; Dafeng Yan; Yafei Li; Jianfeng Jia; Shuangyin Wang

doi:10.1002/anie.202317087

A Universal Approach for Sustainable Urea Synthesis via Intermediate Assembly at the Electrode/Electrolyte Interface

Angew Chem Int Ed Engl. 2024 Jan 15;63(3):e202317087. doi: 10.1002/anie.202317087. Epub 2023 Dec 15.

Authors

Xiaojin Tu¹, Xiaorong Zhu², Shuowen Bo³, Xiaoran Zhang¹, Ruping Miao^{1

4}, Guobin Wen¹, Chen Chen¹, Jing Li⁵, Yangyang Zhou¹, Qinghua Liu³, Dawei Chen^{1

4}, Huaiyu Shao⁵, Dafeng Yan⁶, Yafei Li⁷, Jianfeng Jia⁸, Shuangyin Wang¹

Affiliations

¹ State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, China.
² School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu, P. R. China.
³ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui, P. R. China.
⁴ College of Material Science and Engineering, Qingdao University of Science and Technology, Qingdao, Shandong, P. R. China.
⁵ Guangdong-Hong Kong-Macau Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices, Institute of Applied Physics and Materials Engineering, University of Macau, Avenida da Universidade, Taipa, Macau SAR, 999078, P. R. China.
⁶ College of Chemistry and Chemical Engineering, Hubei University, Wuhan, Hubei, P. R. China.
⁷ College of Chemistry and Materials Science, Nanjing Normal University, Nanjing, Jiangsu, P. R. China.
⁸ Key Laboratory of Magnetic Molecules and Magnetic Information Materials (Ministry of Education), School of Chemistry and Material Science, Shanxi Normal University, Taiyuan, Shanxi, P. R. China.

PMID: 38055225
DOI: 10.1002/anie.202317087

Abstract

Electrocatalytic C-N coupling process is indeed a sustainable alternative for direct urea synthesis and co-upgrading of carbon dioxide and nitrate wastes. However, the main challenge lies in the unactivated C-N coupling process. Here, we proposed a strategy of intermediate assembly with alkali metal cations to activate C-N coupling at the electrode/electrolyte interface. Urea synthesis activity follows the trend of Li⁺ <Na⁺ <Cs⁺ <K⁺ . In the presence of K⁺ , a world-record performance was achieved with a urea yield rate of 212.8±10.6 mmol h^-1 g^-1 on a single-atom Co supported TiO₂ catalyst at -0.80 V versus reversible hydrogen electrode. Theoretical calculations and operando synchrotron-radiation Fourier transform infrared measurements revealed that the energy barriers of C-N coupling were significantly decreased via K⁺ mediated intermediate assembly. By applying this strategy to various catalysts, we demonstrate that intermediate assembly at the electrode/electrolyte interface is a universal approach to boost sustainable urea synthesis.

Keywords: C−N Coupling; Electrode/Electrolyte Interface; Intermediate Assembly; Urea Synthesis.

Abstract

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