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<p>High-entropy alloys (HEAs) are promising electrocatalysts for the hydrogen evolution reaction (HER), offering tunable surface chemistry, multi-site synergy, and stability in alkaline media. In this work, CoCuZnMnNiFe (HEA-0) and its Al-, Cr-, and AlCr-modified derivatives (HEA-A, HEA-C, and HEA-AC) were synthesized via hydrothermal co-reduction followed by annealing. X-ray diffraction (XRD) revealed a dual FCC structure for HEA-0, while Cr- and AlCr-modified alloys showed σ-phase precipitation. SEM/EDS confirmed homogeneous distribution in HEA-0 and morphology changes with Al and Cr addition. X-ray photoelectron spectroscopy (XPS) identified metallic states with Al<sub>2</sub>O<sub>3</sub> and Cr<sub>2</sub>O<sub>3</sub> dominating in modified alloys. Electrochemical tests in 1.0&#xa0;M KOH demonstrated HER activity in the order HEA-0 &gt; HEA-C &gt; HEA-A &gt; HEA-AC. HEA-0 exhibited the lowest onset potential (0.38&#xa0;V vs RHE), smallest Tafel slope (39.27&#xa0;mV&#xa0;dec<sup>−1</sup>), and highest hydrogen yield (~ 1000&#xa0;mmol in 3600&#xa0;s). These findings highlight the balance between electronic modulation and oxide passivation in HEA catalysts.</p>

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Unveiling the impact of Al and Cr alloying on structure and HER performance of CoCuZnMnNiFe high-entropy alloy nanoparticles

  • 期刊论文

  • 发表日期：

    2025年10月29日

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  • Ismail Bencherifa,
  • Ilyas Belkhettab,
  • Khaled Derkaoui,
  • Oussama Dabou,
  • Abdelmounaim Chetoui,
  • Sofiane Latreche,
  • Ismail Daoud

摘要

High-entropy alloys (HEAs) are promising electrocatalysts for the hydrogen evolution reaction (HER), offering tunable surface chemistry, multi-site synergy, and stability in alkaline media. In this work, CoCuZnMnNiFe (HEA-0) and its Al-, Cr-, and AlCr-modified derivatives (HEA-A, HEA-C, and HEA-AC) were synthesized via hydrothermal co-reduction followed by annealing. X-ray diffraction (XRD) revealed a dual FCC structure for HEA-0, while Cr- and AlCr-modified alloys showed σ-phase precipitation. SEM/EDS confirmed homogeneous distribution in HEA-0 and morphology changes with Al and Cr addition. X-ray photoelectron spectroscopy (XPS) identified metallic states with Al2O3 and Cr2O3 dominating in modified alloys. Electrochemical tests in 1.0 M KOH demonstrated HER activity in the order HEA-0 > HEA-C > HEA-A > HEA-AC. HEA-0 exhibited the lowest onset potential (0.38 V vs RHE), smallest Tafel slope (39.27 mV dec−1), and highest hydrogen yield (~ 1000 mmol in 3600 s). These findings highlight the balance between electronic modulation and oxide passivation in HEA catalysts.