Well-defined asymmetric nitrogen/carbon-coordinated single metal sites for carbon dioxide conversion

Senhe Huang; Ziyu Fang; Chenbao Lu; Jichao Zhang; Jie Sun; Huiping Ji; Jinhui Zhu; Xiaodong Zhuang

doi:10.1016/j.jcis.2024.07.064

Well-defined asymmetric nitrogen/carbon-coordinated single metal sites for carbon dioxide conversion

J Colloid Interface Sci. 2024 Dec:675:683-688. doi: 10.1016/j.jcis.2024.07.064. Epub 2024 Jul 8.

Authors

Senhe Huang¹, Ziyu Fang¹, Chenbao Lu², Jichao Zhang³, Jie Sun⁴, Huiping Ji⁵, Jinhui Zhu⁶, Xiaodong Zhuang¹

Affiliations

¹ The Soft2D Lab, State Key Laboratory of Metal Matrix Composites, Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China; Frontiers Science Center for Transformative Molecules, Zhang Jiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai 201203, China.
² The Soft2D Lab, State Key Laboratory of Metal Matrix Composites, Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China; College of Chemistry, Zhengzhou University, Zhengzhou 450001, Henan, China.
³ Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, No. 239, Zhangheng Road, Shanghai 201204, China.
⁴ Carbon Trading Research Center, School of Finance, Shanghai Lixin University of Accounting and Finance, No. 995 Shangchuan Road, Shanghai, China. Electronic address: [email protected].
⁵ Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Institute of Zhejiang University-Quzhou, Zhejiang University, Hangzhou, China. Electronic address: [email protected].
⁶ The Soft2D Lab, State Key Laboratory of Metal Matrix Composites, Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China. Electronic address: [email protected].

PMID: 38996698
DOI: 10.1016/j.jcis.2024.07.064

Abstract

Asymmetric nitrogen/carbon-coordinated single metal sites (M-N_xC_4-x) outperform symmetric M-N₄ sites in carbon dioxide (CO₂) electroreduction. However, the challenge of crafting well-defined M-N_xC_4-x sites complicates the understanding of their structure-catalytic performance relationship. In this study, we employ metallized N-confused tetraphenylporphyrin (M-NCTPP) to investigate CO₂ conversion on M-N₃C₁ sites using both density functional theory and experimental methods. The optimal cobalt (Co)-N₃C₁ site (Co-NCTPP) achieves a current density of 500 mA cm^-² and a carbon monoxide Faraday efficiency exceeding 90 % at -1.25 V vs. the reversible hydrogen electrode, surpassing the performance of Co-N₄ (Co-TPP). This research introduces a novel approach for designing and synthesizing high-activity heteroatom-anchored single metal sites, advancing fundamental understanding in the field.

Keywords: Carbon dioxide electroreduction; Density functional theory calculations; Nitrogen-confused tetraphenylporphyrin; Nitrogen/carbon-coordinated single metal sites; Structure-property relationship.