The coordination environment of carbon-supported metal single-atom catalysts is closely related with the arrangement of heteroatoms, but the preparation of catalysts via pyrolysis usually encounter the collapse of the precursor structure. The accurate manipulation of the coordinative heteroatoms in single-atom catalysts is essential to optimize catalytic performance and further investigation of the catalytic mechanism.

Recently, Prof. Jingqi Tian, Associate Prof. Tengfei Jiang, and Prof. Romain Gautier from Nantes University have proposed a topological heteroatom transfer strategy for tailoring the coordination environment of carbon-supported single-atom catalysts. Based on the self-assembly of graphene quantum dots to form helical fibers in which the hanging groups in the internal cavities can chelate with metal ions (N_x···Mⁿ⁺···O_y), the graphitic characteristics of graphene quantum dots is used to avoid structure collapse during pyrolysis while the heteroatoms are transferred from the assemblies to the single-atom catalysts, realizing the precise arrangement of heteroatoms in carbon-supported single Co atom catalysts (Co-P_xN_4-x-C, x=0, 1, 2, 3). Co-P₂N₂-C exhibits electrocatalytic performance as a non-noble metal single-atom catalyst for alkaline hydrogen evolution. Based on comprehensive characterization for structure analysis combined with theoretical calculations, the electrocatalytic mechanism could be deduced to that the incorporation of specifically coordinated P atoms not only leads to a moderate electron density on Co sites, optimizing *OH adsorption, but also transforms these P atoms into proton-acceptor centers, enhancing the Tafel kinetics and overall HER activity. This work is published in Nat. Commun. with Sheng Qian who is a doctoral student at Yangzhou University as the first author.

Article Information: Sheng Qian, Feng Xu, Yu Fan, Ningyan Cheng, Huaiguo Xue, Ye Yuan, Romain Gautier*, Tengfei Jiang*, Jingqi Tian*, Tailoring coordination environments of single-atom electrocatalysts for hydrogen evolution by topological heteroatom transfer. Nat Commun 15, 2774 (2024).

Link: https://doi.org/10.1038/s41467-024-47061-6.