用于二氧化碳转化的明确不对称氮/碳配位单金属位点

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

作者信息

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

机构信息

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.

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.

出版信息

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

DOI:10.1016/j.jcis.2024.07.064

PMID:38996698

Abstract

Asymmetric nitrogen/carbon-coordinated single metal sites (M-NC) outperform symmetric M-N sites in carbon dioxide (CO) electroreduction. However, the challenge of crafting well-defined M-NC sites complicates the understanding of their structure-catalytic performance relationship. In this study, we employ metallized N-confused tetraphenylporphyrin (M-NCTPP) to investigate CO conversion on M-NC sites using both density functional theory and experimental methods. The optimal cobalt (Co)-NC site (Co-NCTPP) achieves a current density of 500 mA cm and a carbon monoxide Faraday efficiency exceeding 90 % at -1.25 V vs. the reversible hydrogen electrode, surpassing the performance of Co-N (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.

摘要

不对称氮/碳配位单金属位点（M-NC）在二氧化碳（CO₂）电还原方面优于对称的M-N位点。然而，构建明确的M-NC位点面临的挑战使得理解其结构与催化性能的关系变得复杂。在本研究中，我们采用金属化的含氮混乱四苯基卟啉（M-NCTPP），运用密度泛函理论和实验方法研究M-NC位点上的CO₂转化。最佳的钴（Co）-NC位点（Co-NCTPP）在相对于可逆氢电极-1.25 V时实现了500 mA cm⁻²的电流密度和超过90%的一氧化碳法拉第效率，超越了Co-N（Co-TPP）的性能。本研究引入了一种设计和合成高活性杂原子锚定单金属位点的新方法，推动了该领域的基础认识。