Page 32 - Read Online

Zhang et al. J Mater Inf 2024;4:1 Journal of
DOI: 10.20517/jmi.2023.34
Materials Informatics

Research Article Open Access

High hydrogen evolution activities of dual-metal
atoms incorporated N-doped graphenes achieved by

coordination regulation

Cunjin Zhang, Shuaibo Qin, Hui Gao, Peng Jin *
School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, China.
* Correspondence to: Prof. Peng Jin, School of Materials Science and Engineering, Hebei University of Technology, No.
5340, Xiping Road, Beichen District, Tianjin 300130, China. E-mail: pengjin@hebut.edu.cn

How to cite this article: Zhang C, Qin S, Gao H, Jin P. High hydrogen evolution activities of dual-metal atoms incorporated N-
doped graphenes achieved by coordination regulation. J Mater Inf 2024;4:1. https://dx.doi.org/10.20517/jmi.2023.34

Received: 31 Oct 2023 First Decision: 24 Nov 2023 Revised: 13 Dec 2023 Accepted: 27 Dec 2023 Published: 3 Jan 2024
Academic Editors: Jingxiang Zhao, Xingjun Liu, Fengyu Li Copy Editor: Dong-Li Li Production Editor: Dong-Li Li

Abstract
Electrolysis of water to produce hydrogen (H) can solve the current energy crisis and environmental problems.
However, efficient hydrogen evolution reaction (HER) catalysts are still limited to a few noble metals, thus
prohibiting their broad applications. Herein, first-principles calculations were carried out to investigate the
theoretical HER performances of a series of N-doped graphenes containing inexpensive single- and dual-metal
atoms. Among them, MN -gra (M = Fe, Co, Ni), homonuclear MMN -gra, and heteronuclear M1M2N -gra mostly
4 6 6
exhibit low HER activities due to the weak H adsorption, and only CoN -gra, NiNiN -gra, and CoNiN -gra show
4 6 6
better ΔG values of 0.19, 0.15 and 0.27 eV, respectively. In contrast, low-coordinated MMN -gra and M1M2N -gra
*H 5 5
both have rather high HER activities. In particular, the ΔG values of FeNiN -gra and CoNiN -gra are as low as
*H 5 5
-0.04 and -0.06 eV, respectively, very close to the ideal 0 eV. Detailed analyses reveal that such high activity
mainly stems from the reduced metal coordination and the synergistic effect between the two metals, which
greatly enhance the adsorption ability of the active center. More interestingly, the strong H adsorption of
MMN -gra/M1M2N -gra could enable them to further adsorb a second H atom and generate a stable HMH
5
5
intermediate to yield the final product H . Under this novel mechanism, the two-step |ΔG | values of FeNiN -gra
2
5
*H
and CoNiN -gra are all no more than 0.10 eV. Our work not only discloses the important effect of coordination
5
regulation and site synergy on enhancing the catalytic activity but also finds a new HER path on the metal-
embedded N-doped graphenes.
Keywords: Hydrogen evolution reaction, density functional calculations, N-doped graphene, dual-atom catalyst,
coordination regulation

© The Author(s) 2024. Open Access This article is licensed under a Creative Commons Attribution 4.0
International License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, sharing,
adaptation, distribution and reproduction in any medium or format, for any purpose, even commercially, as
long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and
indicate if changes were made.

www.oaepublish.com/jmi