Defect engineering with N-doped carbon hybrid cobalt-molybdenum phosphide nanosheets wrapped molybdenum oxide nanorods for alkaline hydrogen evolution reaction

Yunhua Zheng; Huiting Hu; Long Qian; Yao Zhu; Jian Rong; Tao Zhang; Dongya Yang; Fengxian Qiu

doi:10.1016/j.jcis.2023.09.017

Defect engineering with N-doped carbon hybrid cobalt-molybdenum phosphide nanosheets wrapped molybdenum oxide nanorods for alkaline hydrogen evolution reaction

J Colloid Interface Sci. 2023 Dec 15;652(Pt B):1803-1811. doi: 10.1016/j.jcis.2023.09.017. Epub 2023 Sep 5.

Authors

Yunhua Zheng¹, Huiting Hu¹, Long Qian¹, Yao Zhu¹, Jian Rong², Tao Zhang³, Dongya Yang¹, Fengxian Qiu⁴

Affiliations

¹ School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, 212013, China.
² School of Environmental and Safety Engineering, Changzhou University, Changzhou 213164, China.
³ School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, 212013, China. Electronic address: zhangtaochem@163.com.
⁴ School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, 212013, China. Electronic address: fxqiu@ujs.edu.cn.

PMID: 37683408
DOI: 10.1016/j.jcis.2023.09.017

Abstract

Regulating the electrocatalytic hydrogen evolution reaction (HER) performance through defect engineering of the surface of the catalysts is an effective pathway. Herein, cobalt-molybdenum phosphide (CoMoP) nanosheets wrapped molybdenum oxide (MoO₃) core-shell nanorods (MoO₃@CoMoP), as alkaline electrocatalysts with ligand-derived N-doped carbon hybrid and oxygen-vacancies, were synthesized via solvothermal approaches and followed by phosphorization. As expected, the MoO₃@MoCoP affords efficient HER with a low overpotential (η) of 84.2 ± 0.4 mV at 10 mA cm^-2. After phosphorization, not only the MoCoP active species are incorporated into the catalyst, but also the defects sites are achieved. Impressively, the metal-ligand-derived MoCoP are distributed uniformly in the N-doped carbon hybrid matrix, exhibiting well-exposed active sites. Benefiting from the synergy effect of MoCoP active species and oxygen-vacancy, the MoO₃@MoCoP showed increased conductivity and stability, which can deliver a current density of 10 mA cm^-2 over 40 h. MoO₃@MoCoP exhibits an optimal electronic structure on the surface by charge redistribution at the interface, thereby optimizing the hydrogen adsorption energy and accelerating the hydrogen evolution kinetics. This work paves the way for the design of transition metal electrocatalysts with desirable properties through a promising strategy in the field of energy conversion.

Keywords: Defect engineering; Hydrogen evolution reaction; Nitrogen-doped carbon catalyst; Oxygen vacancy; Transition metal phosphides.