Impact of bimetallic synergies on Mo-doping NiFeOOH: Insights into enhanced OER activity and reconstructed electronic structure

Abstract

NiFe (oxy)hydroxide (NiFeOOH) is recognized as a highly active non-precious metal catalyst in alkaline water electrolysis due to its exceptional catalytic properties. In this work, high valence molybdenum (Mo) is introduced to improve the electronic structure and enhance the electrical conductivity of NiFeOOH for oxygen evolution reaction (OER). The introduction of Mo results in a Mo-doped NiFeOOH catalyst with a significantly reduced overpotential of 205 mV at 10 mA/cm² and a Tafel slope of 31.7 mV/dec, enabling stable operation for up to 170 h. Both empirical experiment and theory simulations are employed to gain insight into the 3d-electron interactions between molybdenum and nickel (Ni), iron (Fe) in Mo-doped NiFeOOH. The results indicate that Mo-doping enhances the valence states of Ni and Fe, leading to a shift in the d-band center of the bimetallic active sites. This modification affects the transformation of Mo-doped NiFeOOH into the γ-NiFeOOH active phase. This potent combination lends credence to its potential suitability and utility in OER applications.

Graphical abstract

Keywords

Mo doping / NiFe (oxy)hydroxide (NiFeOOH) / bimetallic synergies / oxygen evolution reaction (OER) / electronic structure

References

[1] van der Zalm J M, Quintal J, Hira S A. . Recent trends in electrochemical catalyst design for hydrogen evolution, oxygen evolution, and overall water splitting. Electrochimica Acta, 2023, 439: 141715

[2] Rao Y, Wang Y, Ning H. . Hydrotalcite-like Ni(OH)₂ nanosheets in situ grown on nickel foam for overall water splitting. ACS Applied Materials & Interfaces, 2016, 8(49): 33601–33607

[3] Wang X, Tong R, Wang Y. . Surface roughening of nickel cobalt phosphide nanowire arrays/Ni foam for enhanced hydrogen evolution activity. ACS Applied Materials & Interfaces, 2016, 8(50): 34270–34279

[4] Wu H, Huang Q, Shi Y. . Electrocatalytic water splitting: Mechanism and electrocatalyst design. Nano Research, 2023, 16(7): 9142–9157

[5] Tahir M, Pan L, Idrees F. . Electrocatalytic oxygen evolution reaction for energy conversion and storage: A comprehensive review. Nano Energy, 2017, 37: 136–157

[6] Dionigi F, Strasser P. NiFe-based (oxy)hydroxide catalysts for oxygen evolution reaction in non-acidic electrolytes. Advanced Energy Materials, 2016, 6(23): 1600621

[7] McCrory C C L, Jung S, Peters J C. . Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. Journal of the American Chemical Society, 2013, 135(45): 16977–16987

[8] Seh Z W, Kibsgaard J, Dickens C F. . Combining theory and experiment in electrocatalysis: Insights into materials design. Science, 2017, 355(6321): eaad4998

[9] Suen N T, Hung S F, Quan Q. . Electrocatalysis for the oxygen evolution reaction: Recent development and future perspectives. Chemical Society Reviews, 2017, 46(2): 337–365

[10] Oakton E, Lebedev D, Povia M. . IrO₂-TiO₂: A high-surface-area, active, and stable electrocatalyst for the oxygen evolution reaction. ACS Catalysis, 2017, 7(4): 2346–2352

[11] Gao M, Sheng W, Zhuang Z. . Efficient water oxidation using nanostructured α-nickel-hydroxide as an electrocatalyst. Journal of the American Chemical Society, 2014, 136(19): 7077–7084

[12] Chen X, Liu J, Yuan T. . Recent advances in earth-abundant first-row transition metal (Fe, Co and Ni)-based electrocatalysts for the oxygen evolution reaction. Energy Materials, 2022, 2(4): 200028

[13] Yin Z, He R, Zhang Y. . Electrochemical deposited amorphous FeNi hydroxide electrode for oxygen evolution reaction. Journal of Energy Chemistry, 2022, 69: 585–592

[14] He R, Wang C, Feng L. Amorphous FeCoNi-S as efficient bifunctional electrocatalysts for overall water splitting reaction. Chinese Chemical Letters, 2023, 34(2): 107241

[15] Chung D Y, Jun S W, Yoon G. . Large-scale synthesis of carbon-shell-coated FeP nanoparticles for robust hydrogen evolution reaction electrocatalyst. Journal of the American Chemical Society, 2017, 139(19): 6669–6674

[16] Ji L, Wang J, Teng X. . CoP nanoframes as bifunctional electrocatalysts for efficient overall water splitting. ACS Catalysis, 2020, 10(1): 412–419

[17] Zhao S, Xie R, Kang L. . Enhancing hydrogen evolution electrocatalytic performance in neutral media via nitrogen and iron phosphide Interactions. Small Science, 2021, 1(7): 2100032

[18] Fei B, Chen Z, Liu J. . Ultrathinning nickel sulfide with modulated electron density for efficient water splitting. Advanced Energy Materials, 2020, 10(41): 2001963

[19] Wang H, Li J, Li K. . Transition metal nitrides for electrochemical energy applications. Chemical Society Reviews, 2021, 50(2): 1354–1390

[20] Wang Y, Zheng X, Wang D. Design concept for electrocatalysts. Nano Research, 2022, 15(3): 1730–1752

[21] Sha S, Ge R, Li Y. . High-entropy catalysts for electrochemical water-electrolysis of hydrogen evolution and oxygen evolution reactions. Frontiers in Energy, 2024, 18(3): 265–290

[22] Shang Z, Li T, Hu B. . Two-dimensional bimetallic selenium-containing metal-organic frameworks and their calcinated derivatives as electrocatalysts for overall water splitting. Frontiers in Energy, 2024, 18(3): 378–389

[23] Miao L, Guo Z, Jiao L. Insights into the design of mildly acidic aqueous electrolytes for improved stability of Zn anode performance in zinc-ion batteries. Energy Materials, 2023, 3: 300014

[24] Xu L, Cao L, Xu W. . One-step electrosynthesis of NiFe-NF electrodes for highly efficient overall water splitting. Applied Surface Science, 2020, 503: 144122

[25] Zhang B, Wang L, Cao Z. . High-valence metals improve oxygen evolution reaction performance by modulating 3d metal oxidation cycle energetics. Nature Catalysis, 2020, 3(12): 985–992

[26] Jia Z, Yuan Y, Zhang Y. . Optimizing 3d spin polarization of CoOOH by in situ Mo doping for efficient oxygen evolution reaction. Carbon Energy, 2024, 6(1): e418

[27] He Z, Zhang J, Gong Z. . Activating lattice oxygen in NiFe-based (oxy)hydroxide for water electrolysis. Nature Communications, 2022, 13(1): 2191

[28] Tamboli A M, Jung Y, Sim J. . Boosting oxygen evolution reaction activity with Mo incorporated NiFe-LDH electrocatalyst for efficient water electrolysis. Chemosphere, 2023, 344: 140314

[29] Yin Z, Liu X, Cui M. . Template synthesis of molybdenum-doped NiFe-layered double hydroxide nanotube as high efficiency electrocatalyst for oxygen evolution reaction. Mater. Today Sustainability, 2022, 17: 100101

[30] Zheng X, Yang J, Xu Z. . Ru–Co pair sites catalyst boosts the energetics for the oxygen evolution reaction. Angewandte Chemie International Edition, 2022, 61(32): e202205946

[31] Louie M W, Bell A T. An investigation of thin-film Ni–Fe oxide catalysts for the electrochemical evolution of oxygen. Journal of the American Chemical Society, 2013, 135(33): 12329–12337

[32] Liu J, Zheng Y, Jiao Y. . NiO as a bifunctional promoter for RuO₂ toward superior overall water splitting. Small, 2018, 14(16): 1704073

[33] Huang Z F, Song J, Du Y. . Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts. Nature Energy, 2019, 4(4): 329–338

[34] Zhang H, Chen C, Wu X. . Synergistic incorporating RuO₂ and NiFeOOH layers onto Ni₃S₂ nanoflakes with modulated electron structure for efficient water splitting. Small Methods, 2022, 6(9): 2200483

[35] Hall D S, Lockwood D J, Bock C. . Nickel hydroxides and related materials: A review of their structures, synthesis and properties. Proceedings—Royal Society. Mathematical, Physical and Engineering Sciences, 2015, 471(2174): 20140792

[36] Wei L, Du M, Zhao R. . High-valence Mo doping for highly promoted water oxidation of NiFe (oxy)hydroxide. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2022, 10(44): 23790–23798

[37] Xu H, Wang B, Shan C. . Ce-doped NiFe-layered double hydroxide ultrathin nanosheets/nanocarbon hierarchical nanocomposite as an efficient oxygen evolution catalyst. ACS Applied Materials & Interfaces, 2018, 10(7): 6336–6345

[38] Qian L, Lu Z, Xu T. . Trinary layered double hydroxides as high-performance bifunctional materials for oxygen electrocatalysis. Advanced Energy Materials, 2015, 5(13): 1500245

[39] Zhang J, Liu J, Xi L. . Single-atom Au/NiFe layered double hydroxide electrocatalyst: Probing the origin of activity for oxygen evolution reaction. Journal of the American Chemical Society, 2018, 140(11): 3876–3879

[40] Dinh K N, Zheng P, Dai Z. . Ultrathin porous NiFeV ternary layer hydroxide nanosheets as a highly efficient bifunctional electrocatalyst for overall water splitting. Small, 2018, 14(8): 1703257

[41] Yu L, Zhou H, Sun J. . Cu nanowires shelled with NiFe layered double hydroxide nanosheets as bifunctional electrocatalysts for overall water splitting. Energy & Environmental Science, 2017, 10(8): 1820–1827

[42] Wang Y, Zhang Y, Liu Z. . Layered double hydroxide nanosheets with multiple vacancies obtained by dry exfoliation as highly efficient oxygen evolution electrocatalysts. Angewandte Chemie International Edition, 2017, 56(21): 5867–5871

[43] Liu M, Min K A, Han B. . Interfacing or doping? Role of Ce in highly promoted water oxidation of NiFe-layered double hydroxide. Advanced Energy Materials, 2021, 11(33): 2101281

[44] Li P, Duan X, Kuang Y. . Tuning electronic structure of NiFe layered double hydroxides with vanadium doping toward high efficient electrocatalytic water oxidation. Advanced Energy Materials, 2018, 8(15): 1703341

[45] Yang Y, Dang L, Shearer M J. . Highly active trimetallic NiFeCr layered double hydroxide electrocatalysts for oxygen evolution reaction. Advanced Energy Materials, 2018, 8(15): 1703189

[46] Li Y K, Zhang G, Lu W T. . Amorphous Ni–Fe–Mo suboxides coupled with Ni network as porous nanoplate array on nickel foam: A highly efficient and durable bifunctional electrode for overall water splitting. Advanced Science, 2020, 7(7): 1902034

[47] Lu Z, Qian L, Tian Y. . Ternary NiFeMn layered double hydroxides as highly-efficient oxygen evolution catalysts. Chemical Communications, 2016, 52(5): 908–911

[48] Bo X, Hocking R K, Zhou S. . Capturing the active sites of multimetallic (oxy)hydroxides for the oxygen evolution reaction. Energy & Environmental Science, 2020, 13(11): 4225–4237

[49] Gong M, Li Y, Wang H. . An advanced Ni–Fe layered double hydroxide electrocatalyst for water oxidation. Journal of the American Chemical Society, 2013, 135(23): 8452–8455

[50] Liu H, Wang Y, Lu X. . The effects of Al substitution and partial dissolution on ultrathin NiFeAl trinary layered double hydroxide nanosheets for oxygen evolution reaction in alkaline solution. Nano Energy, 2017, 35: 350–357

[51] Zhou D, Cai Z, Jia Y. . Activating basal plane in NiFe layered double hydroxide by Mn²⁺ doping for efficient and durable oxygen evolution reaction. Nanoscale Horizons, 2018, 3(5): 532–537

[52] Jiang J, Sun F, Zhou S. . Atomic-level insight into super-efficient electrocatalytic oxygen evolution on iron and vanadium co-doped nickel (oxy)hydroxide. Nature Communications, 2018, 9(1): 2885

[53] Hu S, Li Y, Kim D. . Surface modulated Fe doping of β-Ni(OH)₂ nanosheets for highly promoted oxygen evolution electrocatalysis. EcoMat, 2022, 4(6): e12256

[54] Hunter B M, Hieringer W, Winkler J R. . Effect of interlayer anions on [NiFe]-LDH nanosheet water oxidation activity. Energy & Environmental Science, 2016, 9(5): 1734–1743

[55] Nørskov J K, Bligaard T, Rossmeisl J. . Towards the computational design of solid catalysts. Nature Chemistry, 2009, 1(1): 37–46

[56] Zhou G, Liu G, Liu X. . 1D/3D heterogeneous assembling body as trifunctional electrocatalysts enabling zinc–air battery and self-powered overall water splitting. Advanced Functional Materials, 2022, 32(4): 2107608

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 52376209), China Postdoctoral Science Foundation (Grant Nos. 2020M673386 and 2020T130503), and China Fundamental Research Funds for the Central Universities.

Competing Interests

The authors declare no competing financial interest.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11708-024-0960-6 and is accessible for authorized users.

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