Ce-induced electronic structure reconfiguration in Ni-based heterostructures for accelerated alkaline hydrogen evolution

IF 9.6 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths Pub Date : 2026-07-01 Epub Date: 2026-04-30 DOI:10.1016/j.jre.2026.04.033

Xuejiao Sun, Hongxi Li, Ji Hua, Xiang Ji, Dongmei Li, Zhongzhen Tian, Ying Liu

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Abstract

This study aimed to develop efficient and stable non-precious metal electrocatalysts for the hydrogen evolution reaction (HER), addressing the limitations of current catalysts such as insufficient activity and high cost. A self-supported CeS/NiS/Ni₃N/SSM electrocatalyst with abundant heterointerfaces was successfully constructed on a stainless steel mesh (SSM) via an electrodeposition combined with high-temperature solid-gas phase sulfidation/nitridation strategy. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses confirm the successful introduction of CeS and the strong electronic interaction among the three phases of CeS, NiS, and Ni₃N. The doping of Ce induces a redistribution of interface charges, forming electron-deficient Ni centers and optimizing the hydrogen adsorption energy. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterizations reveal that the introduction of CeS transforms the smooth agglomerated particles of NiS/Ni₃N into a hierarchical porous structure composed of nanoclusters, significantly increasing the electrochemically active area and constructing clear heterointerfaces, which facilitates the exposure of active sites and mass transfer processes. Density functional theory calculations further indicate that the CeS/NiS/Ni₃N heterostructure exhibits a hydrogen adsorption Gibbs free energy (ΔG_H∗) close to zero (−0.16 eV), significantly superior to that of single components, thereby optimizing the reaction kinetics. The results demonstrate that CeS/NiS/Ni₃N/SSM delivers outstanding HER performance in 1 mol/L KOH, requiring an overpotential of only 73.6 mV to achieve the 10 mA/cm² current density, with a Tafel slope of 87.6 mV/dec, and maintains excellent stability for at least 48 h. This work illustrates that constructing heterointerfaces with simultaneous electronic modulation and structural optimization provides an effective pathway for designing high-performance non-precious metal electrocatalysts.

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镍基异质结构中ce诱导的电子结构重构加速碱氢析出

本研究旨在开发高效、稳定的非贵金属析氢电催化剂，以解决现有催化剂活性不足、成本高的局限。采用电沉积与高温固气相硫化/氮化相结合的方法，在不锈钢网（SSM）上成功构建了具有丰富异质界面的自支撑CeS/NiS/Ni3N/SSM电催化剂。x射线衍射（XRD）和x射线光电子能谱（XPS）分析证实了ce的成功引入以及ce、NiS和Ni3N三个相之间的强电子相互作用。Ce的掺杂引起了界面电荷的重新分配，形成了缺电子的Ni中心，优化了氢的吸附能。扫描电镜（SEM）和透射电镜（TEM）表征表明，ce的引入使光滑的NiS/Ni3N团聚粒子转变为由纳米团簇组成的分层多孔结构，显著增加了电化学活性区域，并构建了清晰的异质界面，有利于活性位点的暴露和传质过程。密度泛函理论计算进一步表明，ce /NiS/Ni3N异质结构的氢吸附吉布斯自由能（ΔGH∗）接近于零（−0.16 eV），明显优于单一组分，从而优化了反应动力学。结果表明，CeS/NiS/Ni3N/SSM在1 mol/L KOH条件下具有优异的HER性能，过电位仅需73.6 mV即可达到10 mA/cm2电流密度，Tafel斜率为87.6 mV/dec，且稳定性至少保持48 h。该研究表明，构建异质界面，同时进行电子调制和结构优化，为设计高性能非贵金属电催化剂提供了有效途径。

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来源期刊

Journal of Rare Earths 化学-应用化学

CiteScore

8.70

自引率

14.30%

发文量

374

审稿时长

1.7 months

期刊介绍： The Journal of Rare Earths reports studies on the 17 rare earth elements. It is a unique English-language learned journal that publishes works on various aspects of basic theory and applied science in the field of rare earths (RE). The journal accepts original high-quality original research papers and review articles with inventive content, and complete experimental data. It represents high academic standards and new progress in the RE field. Due to the advantage of abundant RE resources of China, the research on RE develops very actively, and papers on the latest progress in this field emerge every year. It is not only an important resource in which technicians publish and obtain their latest research results on RE, but also an important way of reflecting the updated progress in RE research field. The Journal of Rare Earths covers all research and application of RE rare earths including spectroscopy, luminescence and phosphors, rare earth catalysis, magnetism and magnetic materials, advanced rare earth materials, RE chemistry & hydrometallurgy, RE metallography & pyrometallurgy, RE new materials, RE solid state physics & solid state chemistry, rare earth applications, RE analysis & test, RE geology & ore dressing, etc.