Acid-stable bimetallic phosphide-silver core-shell nanowires with a seamlessly conductive network for enhanced hydrogen evolution reaction

Hang Yu , Jianhua Zhang , Kailing Zhou , Hao Wang

Front. Energy ›› 2025, Vol. 19 ›› Issue (5) : 694 -702.

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Front. Energy ›› 2025, Vol. 19 ›› Issue (5) : 694 -702. DOI: 10.1007/s11708-025-1023-3
RESEARCH ARTICLE

Acid-stable bimetallic phosphide-silver core-shell nanowires with a seamlessly conductive network for enhanced hydrogen evolution reaction

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Abstract

Developing low-cost and high-performance acid-resistant electrocatalysts is essential for the industrialization of hydrogen production via proton exchange membrane water electrolysis. Herein, an acid-stable bimetal phosphide (NiCoP) catalyst wrapped around silver nanowires (Ag NWs), forming a seamless conductive core-shell structure (NiCoP@Ag NWs), is reported to enhance the hydrogen evolution reaction (HER). The incorporation of Ag NWs creates an uninterrupted conductive network that facilitates efficient electron transfer and provides a large electrolyte-accessible surface area for mass transport. The synergistic interaction among Ni, Co, and P further optimizes electronic structure and decreases the energy barrier of NiCoP@Ag NWs for H* adsorption and desorption. More importantly, the distinctive core-shell structure imparts outstanding acid resistance to the catalyst. Notably, NiCoP@Ag NWs displays remarkable HER performance, with a low overpotential of 109 mV (significantly lower than Ni2P@Ag NWs at 144 mV and Co2P@Ag NWs at 174 mV) at a current density of 10 mA/cm2, along with excellent durability exceeding 100 h in acidic media. These features surpass most reported non-noble metal catalysts, demonstrating extraordinary potential for practical hydrogen production via acidic water electrolysis.

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Keywords

bimetal phosphide / Ag nanowires (Ag NWs) / core-shell structure / hydrogen evolution reaction (HER)

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Hang Yu, Jianhua Zhang, Kailing Zhou, Hao Wang. Acid-stable bimetallic phosphide-silver core-shell nanowires with a seamlessly conductive network for enhanced hydrogen evolution reaction. Front. Energy, 2025, 19(5): 694-702 DOI:10.1007/s11708-025-1023-3

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References

[1]

Gao X , Chen Y , Wang Y . . Next-generation green hydrogen: Progress and perspective from electricity, catalyst to electrolyte in electrocatalytic water splitting. Nano-Micro Letters, 2024, 16(1): 237

[2]

Osman A I , Mehta N , Elgarahy A M . . Hydrogen production, storage, utilisation and environmental impacts: A review. Environmental Chemistry Letters, 2022, 20(1): 153–188

[3]

Liu K , Wu T , Cheng X . . Technical and economic analysis of a pilot-scale hydrogen system: From production to application. Energy Conversion and Management, 2023, 291: 117218

[4]

dos Santos K G , Eckert C T , De Rossi E . . Hydrogen production in the electrolysis of water in Brazil, a review. Renewable & Sustainable Energy Reviews, 2017, 68: 563–571

[5]

Buttler A , Spliethoff H . Current status of water electrolysis for energy storage, grid balancing and sector coupling via power-to-gas and power-to-liquids: A review. Renewable & Sustainable Energy Reviews, 2018, 82: 2440–2454

[6]

Carmo M , Fritz D L , Mergel J . . A comprehensive review on PEM water electrolysis. International Journal of Hydrogen Energy, 2013, 38(12): 4901–4934

[7]

Wu Z Y , Chen F Y , Li B . . Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis. Nature Materials, 2023, 22(1): 100–108

[8]

An L , Wei C , Lu M . . Recent development of oxygen evolution electrocatalysts in acidic environment. Advanced Materials, 2021, 33(20): 2006328

[9]

Kim M , Anjum M A R , Lee M . . Activating MoS2 basal plane with Ni2P nanoparticles for Pt-like hydrogen evolution reaction in acidic media. Advanced Functional Materials, 2019, 29(10): 1809151

[10]

Hansen J N , Prats H , Toudahl K K . . Is there anything better than Pt for HER. ACS Energy Letters, 2021, 6(4): 1175–1180

[11]

Yin J , Jin J , Lin H . . Optimized metal chalcogenides for boosting water splitting. Advanced Science, 2020, 7(10): 1903070

[12]

Staszak-Jirkovský J , Malliakas C D , Lopes P P . . Design of active and stable Co–Mo–Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction. Nature Materials, 2016, 15(2): 197–203

[13]

Garcés-Pineda F A , Blasco-Ahicart M , Nieto-Castro D . . Direct magnetic enhancement of electrocatalytic water oxidation in alkaline media. Nature Energy, 2019, 4(6): 519–525

[14]

Chen W F , Muckerman J T , Fujita E . Recent developments in transition metal carbides and nitrides as hydrogen evolution electrocatalysts. Chemical Communications, 2013, 49(79): 8896–8909

[15]

Chen W F , Sasaki K , Ma C . . Hydrogen-evolution catalysts based on non-noble metal nickel-molybdenum nitride nanosheets. Angewandte Chemie International Edition, 2012, 51(25): 6131–6135

[16]

Park H , Lee E , Lei M . . Canonic-like HER activity of Cr1–xMoxB2 solid solution: overpowering Pt/C at high current density. Advanced Materials, 2020, 32(28): 2000855

[17]

Schmuecker S M , Clouser D , Kraus T J . . Synthesis of metastable chromium carbide nanomaterials and their electrocatalytic activity for the hydrogen evolution reaction. Dalton Transactions, 2017, 46(39): 13524–13530

[18]

Michalsky R , Zhang Y J , Peterson A A . Trends in the hydrogen evolution activity of metal carbide catalysts. ACS Catalysis, 2014, 4(5): 1274–1278

[19]

Chen W F , Wang C H , Sasaki K . . Highly active and durable nanostructured molybdenum carbide electrocatalysts for hydrogen production. Energy & Environmental Science, 2013, 6(3): 943–951

[20]

Xu K , Wang F , Wang Z . . Component-controllable WS2(1–x)Se2x nanotubes for efficient hydrogen evolution reaction. ACS Nano, 2014, 8(8): 8468–8476

[21]

Wang X , Chen Y , Zheng B . . Few-layered WSe2 nanoflowers anchored on graphene nanosheets: A highly efficient and stable electrocatalyst for hydrogen evolution. Electrochimica Acta, 2016, 222: 1293–1299

[22]

Dai W , Wang X , Ma Y . . 2D phosphides heterostructures on titanium microfiltration membrane for enhanced ampere-level current density overall seawater splitting. Nano Research, 2025, 18(1): 94907061

[23]

Boppella R , Tan J , Yang W . . Homologous CoP/NiCoP heterostructure on N-doped carbon for highly efficient and pH-universal hydrogen evolution electrocatalysis. Advanced Functional Materials, 2019, 29(6): 1807976

[24]

Liu P , Rodriguez J A . Catalysts for hydrogen evolution from the [NiFe] hydrogenase to the Ni2P (001) surface: The importance of ensemble effect. Journal of the American Chemical Society, 2005, 127(42): 14871–14878

[25]

Hou Y , Liu Y , Gao R . . Ag@CoxP core-shell heterogeneous nanoparticles as efficient oxygen evolution reaction catalysts. ACS Catalysis, 2017, 7(10): 7038–7042

[26]

Zhang J , Zhou H , Liu Y . . Interface engineering of CoP3/Ni2P for boosting the wide pH range water-splitting activity. ACS Applied Materials & Interfaces, 2021, 13(44): 52598–52609

[27]

Wu L , Yu L , Zhang F . . Heterogeneous bimetallic phosphide Ni2P-Fe2P as an efficient bifunctional catalyst for water/seawater splitting. Advanced Functional Materials, 2021, 31(1): 2006484

[28]

Li D , Zhou C , Yang R . . Interfacial engineering of the CoxP–Fe2P heterostructure for efficient and robust electrochemical overall water splitting. ACS Sustainable Chemistry & Engineering, 2021, 9(23): 7737–7748

[29]

Duan C , Wang L , Liu J . . 3D carbon electrode with hierarchical nanostructure based on NiCoP core-layered double hydroxide shell for supercapacitors and hydrogen evolution. ChemElectroChem, 2021, 8(12): 2272–2281

[30]

Zhou K , Zhang Q , Wang Z . . A Setaria-inflorescence-structured catalyst based on nickel–cobalt wrapped silver nanowire conductive networks for highly efficient hydrogen evolution. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2019, 7(46): 26566–26573

[31]

Jónsson H , Mills G , Jacobsen K W . . Classical and Quantum Dynamics in Condensed Phase Simulations. Singapore: World Scientific, 1998,

[32]

Kresse G , Hafner J . Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Physical Review B: Condensed Matter and Materials Physics, 1994, 49(20): 14251–14269

[33]

Ahrland S , Noren B , Oskarsson A . Crystal structure of iodo (tetrahydrothiophene) gold (I) at 200 K: A compound with an infinite array of gold–gold bonds. Inorganic Chemistry, 1985, 24(9): 1330–1333

[34]

Berland K , Hyldgaard P . Exchange functional that tests the robustness of the plasmon description of the van der Waals density functional. Physical Review B: Condensed Matter and Materials Physics, 2014, 89(3): 035412

[35]

Haider S , Roldan A , de Leeuw N H . Catalytic dissociation of water on the (001), (011), and (111) surfaces of violarite, FeNi2S4: A DFT-D2 study. Journal of Physical Chemistry C, 2014, 118(4): 1958–1967

[36]

Perdew J P , Burke K , Ernzerhof M . Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868

[37]

Methfessel M , Paxton A . High-precision sampling for Brillouin-zone integration in metals. Physical Review B: Condensed Matter and Materials Physics, 1989, 40(6): 3616–3621

[38]

Pulay P . Convergence acceleration of iterative sequences. The case of SCF iteration. Chemical Physics Letters, 1980, 73(2): 393–398

[39]

He L , Gong L , Gao M . . In situ formation of NiCoP@phosphate nanocages as an efficient bifunctional electrocatalyst for overall water splitting. Electrochimica Acta, 2020, 337: 135799

[40]

Wang P , Luo Y , Zhang G . . MnOx-decorated nickel-iron phosphides nanosheets: interface modifications for robust overall water splitting at ultra-high current densities. Small, 2022, 18(7): 2105803

[41]

Bi L , Gao X , Zhang L . . Enhanced photocatalytic hydrogen evolution of NiCoP/g-C3N4 with improved separation efficiency and charge transfer efficiency. ChemSusChem, 2018, 11(1): 276–284

[42]

Xu T , Jiao D , Zhang L . . Br-induced P-poor defective nickel phosphide for highly efficient overall water splitting. Applied Catalysis B: Environmental, 2022, 316: 121686

[43]

Wang Q , Li J , Li Y . . Non-noble metal-based amorphous high-entropy oxides as efficient and reliable electrocatalysts for oxygen evolution reaction. Nano Research, 2022, 15(10): 8751–8759

[44]

Yu J , Zhang Y , Zhang N . . The interface engineering strategy assists the 3D core-shell structure Co3S4/CuS@ NiFe LDH nanocoral spheres to achieve significant overall water splitting. Chinese Chemical Letters, 2025,

[45]

Du C , Yang L , Yang F . . Nest-like NiCoP for highly efficient overall water splitting. ACS Catalysis, 2017, 7(6): 4131–4137

[46]

Sun H , Yu S , Yin J . . Ir doping modulates the electronic structure of flower-shaped phosphides for water oxidation. Inorganic Chemistry, 2024, 63(44): 21283–21292

[47]

Luo Y , Wang P , Zhang G . . Mn-doped nickel–iron phosphide heterointerface nanoflowers for efficient alkaline freshwater/seawater splitting at high current densities. Chemical Engineering Journal, 2023, 454: 140061

[48]

Zhao T , Xu G , Gong B . . Electronic modulation of sprout-shaped NiCoP nanoarrays by N and Ce doping for efficient overall water splitting. Nano Research, 2024, 17(1): 282–289

[49]

Xu M , Han L , Han Y . . Porous CoP concave polyhedron electrocatalysts synthesized from metal-organic frameworks with enhanced electrochemical properties for hydrogen evolution. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2015, 3(43): 21471–21477

[50]

Jiang N , You B , Sheng M . . Electrodeposited cobalt-phosphorous-derived films as competent bifunctional catalysts for overall water splitting. Angewandte Chemie, 2015, 127(21): 6349–6352

[51]

Zhao G , Rui K , Dou S X . . Heterostructures for electrochemical hydrogen evolution reaction: A review. Advanced Functional Materials, 2018, 28(43): 1803291

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