Lattice-expanded NiSe catalyst via lanthanum incorporation for accelerating urea electrooxidation in assisting water electrolysis

doi:10.1016/S1872-2067(26)65054-1

Abstract

Abstract:

Developing bifunctional electrocatalysts for energy-efficient urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) is critical for sustainable hydrogen production and wastewater remediation, yet hindered by sluggish kinetics and insufficient active sites. Herein, we propose demonstrate that lanthanum (La) doping effectively activates nickel selenide (NiSe) by inducing lattice expansion—substituting smaller Ni²⁺ (0.69 Å) with larger La³⁺ ion (1.16 Å)—thereby modulating its electronic structure. The optimized La-NiSe-2 catalyst exhibits markedly enhanced UOR and HER performance: it achieves a UOR current density of 213 mA cm^-2 at 1.6 V vs. RHE (twice that of pristine NiSe) and requires only 135 mV overpotential for HER at -10 mA cm^-2, with a Tafel slope of 78 mV dec^-1. Operando electrochemical impedance spectroscopy and density functional theory calculations reveal that La incorporation enhances charge transfer and strengthens urea adsorption. This work highlights rare-earth-mediated electronic modulation as a viable strategy for designing high-performance bifunctional catalysts for urea-assisted energy and environmental applications.

Key words: Lanthanum doping, Nickelous selenide, Bifunctional electrocatalyst, Urea electrooxidation, Water electrolysis

Quan Zhang, Hejin Ma, Ruobing Han, Tonglin Yang, Zhenhui Chen, Miaoyang Zhu, Jiawei Shi, Weiwei Cai, Fangqi Yang, Zehui Yang. Lattice-expanded NiSe catalyst via lanthanum incorporation for accelerating urea electrooxidation in assisting water electrolysis[J]. Chinese Journal of Catalysis, 2026, 86: 254-264.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65054-1

https://www.cjcatal.com/EN/Y2026/V86/I7/254

Figures/Tables 5

Fig. 1. (a) Synthetic route for La-NiSe electrocatalysts. (b) XRD patterns of the La-NiSe series and NiSe electrocatalysts. Ni 2p (c), La 3d (d), and Se 3d (e) XPS spectra for La-NiSe-2.

Fig. 2. SEM image (a), SEM-EDS spectrum (inset is the atomic ratio) (b), and corresponding EDS mapping images (c) of La-NiSe-2. TEM (d) and HRTEM (e) images (the inset is lattice-spacing analysis) of pure NiSe. TEM (f) and HRTEM images (the inset is lattice-spacing analysis) (g) of La-NiSe-2.

Fig. 3. LSV curves (a) and Tafel slopes (b) for the La-NiSe series, NiSe, Pt/C and RuO2 electrocatalysts in 1 mol L-1 KOH + 0.33 mol L-1 urea electrolyte. (c) Comparison of LSV curves of La-NiSe-2 in 1 mol L-1 KOH with and without 0.33 mol L-1 urea electrolyte. Bode plots of operando EIS of La-NiSe-2 in 1 mol L-1 KOH without (d) and with (e) 0.33 mol L-1 urea solution. (f) LSV curves for La-NiSe-2 before and after 5000 CV cycles, with the corresponding chronopotentiometry stability curve measured in 1 mol L-1 KOH with 0.33 mol L-1 urea shown as the inset.

Fig. 4. LSV curves (a), Tafel slopes (b), ECSAs (c), and EIS curves (d) of the La-NiSe series, NiSe and Pt/C electrocatalysts in 1 mol L-1 KOH with 0.33 mol L-1 urea electrolyte. (e) LSV curves for La-NiSe-2 before and after 5000 cycles. (f) Chronoamperometric stability measurement was measured in 1 mol L-1 KOH + 0.33 mol L-1 urea solution.

Fig. 5. (a) PDOS of the La-NiSe system, with the Fermi level set to zero energy. (b) Differential charge density of La-NiSe; where yellow and blue iso-surfaces (set at ±0.002 e ?-3) represent electron accumulation and depletion, respectively. (c) The adsorption energy of CO(NH2)2 anchored on NiSe and La-NiSe. (d) Urea oxidation pathways and the corresponding energy profiles for La-NiSe. (e) CO2-TPD curves for NiSe and La-NiSe-2 electrocatalysts.

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