A novel tetragonal T-C2N supported transition metal atoms as superior bifunctional catalysts for OER/ORR: From coordination environment to rational design

Zhe Xue; Rui Tan; Hongxia Wang; Jinzhong Tian; Xiaolin Wei; Hua Hou; Yuhong Zhao

doi:10.1016/j.jcis.2023.07.128

A novel tetragonal T-C₂N supported transition metal atoms as superior bifunctional catalysts for OER/ORR: From coordination environment to rational design

J Colloid Interface Sci. 2023 Dec:651:149-158. doi: 10.1016/j.jcis.2023.07.128. Epub 2023 Jul 28.

Authors

Zhe Xue¹, Rui Tan², Hongxia Wang¹, Jinzhong Tian¹, Xiaolin Wei³, Hua Hou⁴, Yuhong Zhao⁵

Affiliations

¹ School of Materials Science and Engineering, Collaborative Innovation Center of Ministry of Education and Shanxi Province for High-performance Al/Mg Alloy Materials, North University of China, Taiyuan 030051, China.
² Physics and Electronic Engineering, Hengyang Normal University, Hengyang 421002, China.
³ Physics and Electronic Engineering, Hengyang Normal University, Hengyang 421002, China. Electronic address: xlw@xtu.edu.cn.
⁴ School of Materials Science and Engineering, Collaborative Innovation Center of Ministry of Education and Shanxi Province for High-performance Al/Mg Alloy Materials, North University of China, Taiyuan 030051, China; School of Materials Science and Engineering, Taiyuan University of Science and Technology, Taiyuan 030024, China.
⁵ School of Materials Science and Engineering, Collaborative Innovation Center of Ministry of Education and Shanxi Province for High-performance Al/Mg Alloy Materials, North University of China, Taiyuan 030051, China; Beijing Advanced Innovation Center for Materials Genome Engineering, University of Science and Technology Beijing, Beijing 100083, China; Institute for Materials Intelligent Technology, Liaoning Academy of Materials, Shenyang 110010, China. Electronic address: zhaoyuhong@nuc.edu.cn.

PMID: 37542890
DOI: 10.1016/j.jcis.2023.07.128

Abstract

Single-atom catalysts with particular electronic structures and precisely regulated coordination environments delivering excellent activity for oxygen-evolution reaction (OER) and oxygen-reduction reaction (ORR) are highly desirable for renewable energy applications. In this work, a novel tetragonal carbon nitride T-C₂N monolayer with remarkable stability was predicted by using the RG² method. Inspired by the well-defined atomic structures and just right N₄ aperture of T-C₂N substrate, the electrocatalytic performance of a series of transition metal single-atoms anchored on porous T-C₂N matrix (TM@C₂N) have been systematically investigated. In addition, machine learning (ML) method was employed with the gradient boosting regression GBR model to deeply explore the complex controlling factors and offer direct guidance for rational discovery of desirable catalysts. On this basis, the coordination environment of the central TM active sites has been tailored by incorporating heteroatoms. Impressively, the Co@C₂N/B-C, Rh@C₂N/SC and Rh@C₂N/SN exhibit significantly enhanced OER/ORR activity with notably low η^OER/η^ORR of 0.39/0.32, 0.26/0.35 and 0.37/0.27 V, respectively. Our work provides insights into the rational design, data-driven, performance regulation, mechanism analysis and practical application of TMNC catalysts. Such a systematic theoretical framework can also be expanded to many other kinds of catalysts for energy storage and conversion.

Keywords: Coordination environment; Density functional theory calculations; Machine learning; Single-atom catalysts; Tetragonal carbon nitride.