Hierarchical nitride/phosphide heterostructure for efficient and ultrastable Ampere-level hydrogen production

doi:10.1016/S1872-2067(26)65173-X

Abstract

Abstract:

Towards large-scale hydrogen production via water splitting, it is crucial to enhance the mechanical stability of electrocatalysts while maximizing the formation and utilization of efficient active sites through rational morphological design and electronic modulation. Here, a hierarchical nitride/phosphide heterostructure electrocatalyst is successfully constructed, consisting of amorphous 2D NiCoP nanosheets vertically grown on crystalline 1D NiMoN nanorod arrays. This unique structure facilitates the formation and exposure of efficient active sites while endowing NiMoN/NiCoP catalyst with a highly hydrophilic and superaerophobic surface. Accordingly, it exhibits an ultralow overpotential of 126 mV at 1000 mA cm^-2 for the hydrogen evolution reaction (HER) in 1 mol L^-1 KOH. Notably, as a bifunctional catalyst, it requires merely 1.74 V in 1 mol L^-1 KOH solution and 1.77 V in an anion exchange membrane water electrolyzer (AEMWE) to achieve 1000 mA cm^-2 of current density, while maintaining stable electrolysis for up to 1600 and 300 h, respectively. Theoretical calculations indicate the interaction between NiMoN and NiCoP leads to the redistribution of charge density. This promotes H₂O adsorption and dissociation, also optimizes the adsorption of H^* intermediates at the heterointerfacial Ni sites, consequently improving the HER activity. These characteristics highlight its promising applicability as an Ampere-level catalyst for hydrogen production.

Key words: Transition metal nitride/phosphide, Hierarchical structures, Heterostructures, Hydrogen production, Water splitting

Zhirong Ren, Haihan Zhou, Tanyuan Wang, Hua-Jin Zhai, Qing Li. Hierarchical nitride/phosphide heterostructure for efficient and ultrastable Ampere-level hydrogen production[J]. Chinese Journal of Catalysis, 2026, 89: 184-195.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65173-X

https://www.cjcatal.com/EN/Y2026/V89/I10/184

Figures/Tables 5

Fig. 1. (a) Schematic diagram of the preparation process for NiMoN/NiCoP catalyst. (b) XRD patterns for NiCoP, NiMoN, and NiMoN/NiCoP. SEM (c,d) and TEM (e,f) images of NiMoN/NiCoP. (g) HR-TEM image and (inset) SAED pattern of NiMoN/NiCoP. (h) HAADF-STEM image and the corresponding EDS mappings of NiMoN/NiCoP.

Fig. 2. High-resolution XPS spectra of Ni 2p (a), Mo 3d (b), Co 2p (c), P 2p (d), and N 1s (e) for the as-prepared catalysts. (f) Nitrogen adsorption-desorption isotherm and (inset) pore-size distribution curve of NiMoN/NiCoP. (g) 1 mol L-1 KOH droplets wetting process (the upper section) and underwater gas-bubble contact angles (the lower section) on NiMoN/NiCoP, NiMoN, NiCoP, and pristine NF.

Fig. 3. Electrocatalytic performance in 1 mol L-1 KOH for various catalysts. (a) LSV curves for HER. (b) Comparison of overpotentials at various current densities. (c) LSV curves for OER. (d) Tafel plots for HER. (e) Comprehensive comparisons of the HER and OER performance. (f) Tafel plots for OER. (g) Chronoamperometry curves for stability test of NiMoN/NiCoP towards HER and OER.

Fig. 4. Electrocatalytic performance of overall water splitting and AEMWE. (a) Polarization curves with iR compensation of NiMoN/NiCoP || NiMoN/NiCoP and Pt/C || RuO2 under laboratory conditions. (b) Comparison of the electrocatalytic performance between NiMoN/NiCoP and other advanced electrocatalysts at the current densities of 100, 500, and 1000 mA cm-2 under laboratory conditions. In this bubble chart, the x-axis is divided into three equal segments representing different current densities, and the y-axis denotes the voltage. The bubbles of various colors correspond to different catalysts, with the bubble area representing the operational duration at the corresponding current density. (c) Stability tests for laboratory conditions and AEMWE. (d) Operation diagram of green energy-driven hydrogen production systems via water splitting with NiMoN/NiCoP electrocatalyst, including solar cell, wind-driven generator, thermoelectric generator, and lithium cells. (e) Polarization curves without iR compensation for the AEMWE with NiMoN/NiCoP || NiMoN/NiCoP and Pt/C || RuO2. (f) Schematic illustration of the AEMWE.

Fig. 5. (a) Optimized structure of NiMoN/NiCoP, in which bluish violet, magenta, bluish green, deep grey, and light blue balls represent the Mo, Co, Ni, P, and N atoms, respectively. (b) PDOS of NiMoN/NiCoP, NiMoN, and NiCoP. (c,d) Charge density difference diagrams of NiMoN/NiCoP with side view. Calculated H2O dissociation (e) and *H adsorption free energy (f) diagrams for NiMoN/NiCoP, NiMoN, and NiCoP.

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