April 13, 2024
Journal Article

One-Step Synthesis and Operando Electrochemical Impedance Spectroscopic Characterization of Heterostructured MoP-Mo2N Electrocatalysts for Stable Hydrogen Evolution Reaction

Abstract

This study presents a novel synthesis of self-standing MoP and Mo2N heterostructured electrocatalysts with enhanced stability and catalytic performance. Facilitated by the controlled phase and interfacial microstructure, the seamless structures of these catalysts minimize internal resistivity and prevent local corrosion, contributing to increased stability. The chemical synthesis proceeds with etching step to activate the surface, followed by phosphor-nitriding in a chemical vapor deposition chamber to produce MoP-Mo2N@Mo heterostructured electrocatalysts. X-ray diffraction analyses confirm the presence of MoP, Mo2N, and Mo phases in the electrocatalyst. Morphology studies using scanning electron microscopy characterizes the hierarchical growth of structures, indicating successful formation of the heterostructure. X-ray photoelectron spectroscopy (XPS) analyses of the as-synthesized and post-catalytic activity samples reveal the chemical shift in terms of binding energy (BE) of Mo 3d XPS peak, especially after catalytic activity. The XPS BE shifts attributed to changes in oxidation state, electron transfer, and surface reconstruction during catalysis. Electrochemical evaluation of the catalysts demonstrates the superior performance of the MoP-Mo2N@Mo heterostructured catalyst in hydrogen evolution reactions (HER), with lower overpotentials and enhanced Tafel slopes. Stability tests reveal changes in double layer capacitance over time, suggesting surface reconstruction and increased active surface area during catalysis. Operando electrochemical impedance spectroscopy (EIS) further elucidates the dynamic changes in resistance and charge transfer during HER. Overall, comprehensive understanding of the synthesis, characterization, and electrochemical behavior of the developed MoP-Mo2N@Mo heterostructured electrocatalyst as presented in this paper highlights their potential utilization in sustainable energy applications.

Published: April 13, 2024

Citation

Attarzadeh N., A. Lakshmi-Narayana, D. Das, S. Tan, V. Shutthanandan, and C. Ramana. 2024. One-Step Synthesis and Operando Electrochemical Impedance Spectroscopic Characterization of Heterostructured MoP-Mo2N Electrocatalysts for Stable Hydrogen Evolution Reaction. ACS Applied Materials & Interfaces 16, no. 6:6958–6970. PNNL-SA-194810. doi:10.1021/acsami.3c14160

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