Ultrafast laser synthesis of sub-10 nm FeCoNiMnCr high-entropy alloy nanoparticles for enhanced oxygen evolution catalysis

Abstract

The development of efficient and robust oxygen non-precious catalysts for the oxygen evolution reaction (OER) remains a critical scientific hurdle in realizing cost-effective renewable energy conversion systems. Herein, we present a rapid laser irradiation synthesis strategy for the successful fabrication of sub-10 nm FeCoNiMnCr high-entropy alloy nanoparticles (HEA-NPs) on multi-wall carbon nanotube (MWCNT) paper, serving as highly efficient OER electrocatalysts. The synthesis of high-entropy alloy nanoparticles with precise control was accomplished through systematic optimization of laser processing parameters. Structural characterization via X-ray diffraction, high-resolution transmission electron microscopy, and high-angle annular dark-field scanning transmission electron microscopy collectively verified the formation of a phase-pure face-centered cubic crystal structure with homogeneous elemental mixing at the atomic scale. Furthermore, COMSOL Multiphysics simulations confirm that this rapid and discontinuous laser irradiation approach enables the precursor material to undergo ultrafast heating and quenching processes, effectively suppressing Ostwald ripening phenomena, which is conducive to the formation of ultrafine (sub-10 nm) high-entropy alloy nanoparticles. The synthesized HEA-NPs catalyst demonstrates exceptional oxygen evolution activity in alkaline electrolyte (1 M KOH), achieving a current density of 10 mA·cm⁻² at a low overpotential of 255 mV while maintaining remarkable stability with negligible activity decay during prolonged operation (>100 h), representing state-of-the-art performance among non-precious metal catalysts. This study provides perspectives on the rapid preparation and performance regulation of HEA-NPs catalysts.

Keywords

oxygen evolution reaction / high-entropy alloy nanoparticles / electrocatalyst / laser

References

[1] Jamesh MI, Sun XM. Recent progress on earth abundant electrocatalysts for oxygen evolution reaction (OER) in alkaline medium to achieve efficient water splitting–A review. J. Power Sources, 2018, 400: 31

[2] Z.J. Chen, S.N. Yun, L. Wu, et al., Waste-derived catalysts for water electrolysis: Circular economy-driven sustainable green hydrogen energy, Nano-Micro Lett., 15(2022), No. 1, art. No. 4.

[3] X. Li, L.L. Zhao, J.Y. Yu, et al., Water splitting: From electrode to green energy system, Nano-Micro Lett., 12(2020), No. 1, art. No. 131.

[4] Sharshir SW, Joseph A, Elsayad MM, Tareemi AA, Kandeal AW, Elkadeem MR. A review of recent advances in alkaline electrolyzer for green hydrogen production: Performance improvement and applications. Int. J. Hydrogen Energy, 2024, 49: 458

[5] Tüysüz H. Alkaline water electrolysis for green hydrogen production. Acc. Chem. Res., 2024, 57(4558

[6] Hu CL, Zhang L, Gong JL. Recent progress made in the mechanism comprehension and design of electrocatalysts for alkaline water splitting. Energy Environ. Sci., 2019, 12(92620

[7] Chen ZB, Huang K, Zhang BW, et al.. Corrosion engineering on AlCoCrFeNi high-entropy alloys toward highly efficient electrocatalysts for the oxygen evolution of alkaline seawater. Int. J. Miner. Metall. Mater., 2023, 30(101922

[8] X.R. Ren, Y.Y. Zhai, N. Yang, B.L. Wang, and S.Z. Liu, Lattice oxygen redox mechanisms in the alkaline oxygen evolution reaction, Adv. Funct. Mater., 34(2024), No. 32, art. No. 2401610.

[9] Han WW, Cai XN, Liao JH, He Y, Yu CL, Zhang XW. Regulating strain and electronic structure of indium tin oxide supported IrOx electrocatalysts for highly efficient oxygen evolution reaction in acid. ACS Appl. Mater. Interfaces, 2024, 16(3647610

[10] R. Qin, G.Z. Chen, X.T. Feng, J.N. Weng, and Y.H. Han, Ru/Ir-based electrocatalysts for oxygen evolution reaction in acidic conditions: From mechanisms, optimizations to challenges, Adv. Sci., 11(2024), No. 21, art. No. 2309364.

[11] Li L, Cao XJ, Huo JJ, et al.. High valence metals engineering strategies of Fe/Co/Ni-based catalysts for boosted OER electrocatalysis. J. Energy Chem., 2023, 76: 195

[12] A. Ahmad, A. Nairan, Z. Feng, et al., Unlocking the potential of high entropy alloys in electrochemical water splitting: A review, Small, 20(2024), No. 29, art. No. 2311929.

[13] J.H. Chen, J.L. Ma, T. Huang, et al., Iridium-free high-entropy alloy for acidic water oxidation at high current densities, Angew. Chem. Int. Ed., 137(2025), No. 21, art. No. e202503330.

[14] S.Q. Wang, W.Y. Huo, F. Fang, Z.H. Xie, J.K. Shang, and J.Q. Jiang, High entropy alloy/C nanoparticles derived from poly-metallic MOF as promising electrocatalysts for alkaline oxygen evolution reaction, Chem. Eng. J., 429(2022), art. No. 132410.

[15] K. Li and W. Chen, Recent progress in high-entropy alloys for catalysts: Synthesis, applications, and prospects, Mater. Today Energy, 20(2021), art. No. 100638.

[16] Sharma L, Katiyar NK, Parui A, et al.. Low-cost high entropy alloy (HEA) for high-efficiency oxygen evolution reaction (OER). Nano Res., 2022, 15(64799

[17] Mthisi A, Malatji N, Patricia A, Popoola I, Kanyane LR. Parametric study of spark plasma sintering of Al₂₀Cr₂₀Fe₂₅Ni₂₅Mn₁₀ high entropy alloy with improved micro-hardness and corrosion. Int. J. Miner. Metall. Mater., 2022, 29(1119

[18] Yang Y, Song BA, Ke X, et al.. Aerosol synthesis of high entropy alloy nanoparticles. Langmuir, 2020, 36(81985

[19] M. Bondesgaard, N.L.N. Broge, A. Mamakhel, M. Bremholm, and B.B. Iversen, General solvothermal synthesis method for complete solubility range bimetallic and high-entropy alloy nanocatalysts, Adv. Funct. Mater., 29(2019), No. 50, art. No. 1905933.

[20] Yao YG, Huang ZN, Xie PF, et al.. Carbothermal shock synthesis of high-entropy-alloy nanoparticles. Science, 2018, 359(63831489

[21] K. Huang, D.D. Peng, Z.X. Yao, et al., Cathodic plasma driven self-assembly of HEAs dendrites by pure single FCC FeCoNiMnCu nanoparticles as high efficient electrocatalysts for OER, Chem. Eng. J., 425(2021), art. No. 131533.

[22] Xia JY, Zhang JH, Huang K, et al.. In situ growth of an active catalytic layer on commercial stainless steel via a hydrothermal-assisted corrosion process for efficient oxygen evolution reaction. J. Mater. Chem. A, 2024, 12(3019008

[23] J.Y. Xia, K. Huang, Z.X. Yao, et al., Ternary duplex FeCoNi alloy prepared by cathode plasma electrolytic deposition as a high-efficient electrocatalyst for oxygen evolution reaction, J. Alloy. Compd., 891(2022), art. No. 161934.

[24] George EP, Raabe D, Ritchie RO. High-entropy alloys. Nat. Rev. Mater., 2019, 4(8515

[25] Takeuchi A, Inoue A. Classification of bulk metallic glasses by atomic size difference, heat of mixing and period of constituent elements and its application to characterization of the main alloying element. Mater. Trans., 2005, 46(122817

[26] J.H. Zhang, Y. Lu, M.Z. Xiu, et al., Mg-evaporation induced amorphous multi-principal element alloys for advanced oxygen evolution reaction, Nano Energy, 136(2025), art. No. 110686.

[27] Zhang Z, Zhou F, Lavernia EJ. On the analysis of grain size in bulk nanocrystalline materials via X-ray diffraction. Metall. Mater. Trans. A, 2003, 34(61349

[28] Joo SH, Park JY, Renzas JR, Butcher DR, Huang WY, Somorjai GA. Size effect of ruthenium nanoparticles in catalytic carbon monoxide oxidation. Nano Lett., 2010, 10(72709

[29] Cuenya BR, Behafarid F. Nanocatalysis: Size- and shape-dependent chemisorption and catalytic reactivity. Surf. Sci. Rep., 2015, 70(2135

[30] Skala DU, Saban MD, Orlovic AM, et al.. Hydrotreating of used oil: Prediction of industrial trickle-bed operation from pilot-plant data. Ind. Eng. Chem. Res., 1991, 30(92059

[31] Y. Lu, K. Huang, X. Cao, et al., Atomically dispersed intrinsic hollow sites of M–M₁–M (M₁ = Pt, Ir; M = Fe, Co, Ni, Cu, Pt, Ir) on FeCoNiCuPtIr nanocrystals enabling rapid water redox, Adv. Funct. Mater., 32(2022), No. 19, art. No. 2110645.

[32] Huang K, Zhang BW, Wu JS, et al.. Exploring the impact of atomic lattice deformation on oxygen evolution reactions based on a sub 5 nm pure face-centred cubic high-entropy alloy electrocatalyst. J. Mater. Chem. A, 2020, 8(2411938

[33] K. Huang, X. Cao, Y. Lu, et al., Lattice-disordered high-entropy alloy engineered by thermal dezincification for improved catalytic hydrogen evolution reaction, Adv. Mater., 36(2024), No. 32, art. No. 2304867.

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