Tailoring coordination environments of single-atom electrocatalysts for hydrogen evolution by topological heteroatom transfer

Sheng Qian; Feng Xu; Yu Fan; Ningyan Cheng; Huaiguo Xue; Ye Yuan; Romain Gautier; Tengfei Jiang; Jingqi Tian

doi:10.1038/s41467-024-47061-6

Tailoring coordination environments of single-atom electrocatalysts for hydrogen evolution by topological heteroatom transfer

Nat Commun. 2024 Mar 30;15(1):2774. doi: 10.1038/s41467-024-47061-6.

Authors

Sheng Qian¹, Feng Xu¹, Yu Fan¹, Ningyan Cheng², Huaiguo Xue¹, Ye Yuan³, Romain Gautier⁴, Tengfei Jiang⁵, Jingqi Tian⁶

Affiliations

¹ School of Chemistry and Chemical Engineering, Yangzhou University, 180 Si-Wang-Ting Road, Yangzhou, 225002, P. R. China.
² Information Materials and Intelligent Sensing Laboratory of Anhui Province, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology, Anhui University, Hefei, 230601, P. R. China.
³ Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, P. R. China.
⁴ Nantes Université, CNRS, Institut des Matériaux de Nantes Jean Rouxel, IMN, F-44000, Nantes, France. romain.gautier@cnrs-imn.fr.
⁵ School of Chemistry and Chemical Engineering, Yangzhou University, 180 Si-Wang-Ting Road, Yangzhou, 225002, P. R. China. jiangtengfei@yzu.edu.cn.
⁶ School of Chemistry and Chemical Engineering, Yangzhou University, 180 Si-Wang-Ting Road, Yangzhou, 225002, P. R. China. tianjq@yzu.edu.cn.

Abstract

The rational design of carbon-supported transition-metal single-atom catalysts requires the precise arrangement of heteroatoms within the single-atom catalysts. However, achieving this design is challenging due to the collapse of the structure during the pyrolysis. Here, we introduce a topological heteroatom-transfer strategy to prevent the collapse and accurately control the P coordination in carbon-supported single-atom catalysts. As an illustration, we have prepared self-assembled helical fibers with encapsulated cavities. Within these cavities, adjustable functional groups can chelate metal ions (N_x···Mⁿ⁺···O_y), facilitating the preservation of the structure during the pyrolysis based phosphidation. This process allows for the transfer of heteroatoms from the assembly into single-atom catalysts, resulting in the precise coordination tailoring. Notably, the Co-P₂N₂-C catalyst exhibits electrocatalytic performance as a non-noble metal single-atom catalyst for alkaline hydrogen evolution, attaining a current density of 100 mA cm^-2 with an overpotential of only 131 mV.