Efficient C-N coupling for urea electrosynthesis on defective Co3O4 with dual-functional sites

Pengsong Li; Qinggong Zhu; Jiyuan Liu; Tianbin Wu; Xinning Song; Qinglei Meng; Xinchen Kang; Xiaofu Sun; Buxing Han

doi:10.1039/d3sc06579k

Efficient C-N coupling for urea electrosynthesis on defective Co₃O₄ with dual-functional sites

Chem Sci. 2024 Jan 18;15(9):3233-3239. doi: 10.1039/d3sc06579k. eCollection 2024 Feb 28.

Authors

Pengsong Li^{1

2}, Qinggong Zhu^{1

2}, Jiyuan Liu^{1

2}, Tianbin Wu^{1

2}, Xinning Song^{1

2}, Qinglei Meng^{1

2}, Xinchen Kang^{1

2}, Xiaofu Sun^{1

2}, Buxing Han^{1

2

3}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences Beijing 100190 China qgzhu@iccas.ac.cn hanbx@iccas.ac.cn.
² School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences Beijing 100049 China.
³ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University Shanghai 200062 China.

Abstract

Urea electrosynthesis under ambient conditions is emerging as a promising alternative to conventional synthetic protocols. However, the weak binding of reactants/intermediates on the catalyst surface induces multiple competing pathways, hindering efficient urea production. Herein, we report the synthesis of defective Co₃O₄ catalysts that integrate dual-functional sites for urea production from CO₂ and nitrite. Regulating the reactant adsorption capacity on defective Co₃O₄ catalysts can efficiently control the competing reaction pathways. The urea yield rate of 3361 mg h^-1 g_cat^-1 was achieved with a corresponding faradaic efficiency (FE) of 26.3% and 100% carbon selectivity at a potential of -0.7 V vs. the reversible hydrogen electrode. Both experimental and theoretical investigations reveal that the introduction of oxygen vacancies efficiently triggers the formation of well-matched adsorption/activation sites, optimizing the adsorption of reactants/intermediates while decreasing the C-N coupling reaction energy. This work offers new insights into the development of dual-functional catalysts based on non-noble transition metal oxides with oxygen vacancies, enabling the efficient electrosynthesis of essential C-N fine chemicals.