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[目的]非贵金属Ni基电催化剂是一类重要的碱性电解水电极材料，探索Ni基析氢和析氧双功能催化剂的优化策略是提升氢能作为新能源核心竞争力的关键。[方法]通过Cu和Cr共掺杂对Ni基催化剂的表面电子结构进行协同调制，采用浸渍法结合H2/Ar高温还原，制备了对析氢反应(HER)有良好活性的NiCuCr/C合金催化剂。再引入柠檬酸(CA)和尿素(U)调控表界面性质，以提升其析氧反应(OER)性能。利用X射线衍射(XRD)、透射电镜(TEM)、X射线光电子能谱(XPS)及电化学测试，对催化剂的物相结构、微观形貌、表面电子态和电催化性能进行了表征，以阐明构效关系。[结果]优化的Ni Cu0.1Cr0.02/C催化剂在1.0 mol/L KOH溶液中展现出优异的HER活性，在10 mA/cm2电流密度下的过电位为174 mV。Cu和Cr共掺杂可促进电子向表面Ni活性中心转移，显著提升表面电子密度，并优化氢中间体的吸附-解吸动力学。经CA-U形貌调控所得到的Ni Cu0.05Cr0.02/CA-U催化剂具有良好的OER性能，在10 mA/cm2电流密度下的过电位为348 mV，优于含Ru的对比催化剂Ru0.03Ni Cu0.05Cr0.02/CA-U。[结论]通过多组分和形貌调节剂策略实现了Ni Cu Cr三元合金催化剂的制备及其表面电子结构调控，该材料展现了良好的HER和OER性能，为开发低成本、高效的双功能镍基电催化剂提供了新思路。
Abstract：[Objective] Non-noble metal Ni-based electrocatalysts represent an important class of electrode materials for alkaline water electrolysis. Exploring optimization strategies for bifunctional Ni-based catalysts for both hydrogen evolution reaction(HER) and oxygen evolution reaction(OER) is crucial for enhancing the core competitiveness of hydrogen energy as a new energy source. [Method] The surface electronic structure of Ni-based catalysts was synergistically modulated by Cu and Cr co-doping. NiCuCr/C alloy catalysts with good activity for HER were prepared by impregnation combined with H2/Ar high-temperature reduction. Citric acid(CA) and urea(U) were then introduced to regulate the surface and interface properties to enhance the OER performance. The phase structure, microstructure, surface electronic states, and electrocatalytic performance of the catalysts were characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), and electrochemical tests to clarify the structure-activity relationship. [Result] The optimized NiCu0.1Cr0.02/C catalyst exhibited excellent HER activity in 1.0 mol/L KOH solution, with an overpotential of 174 mV at a current density of 10 mA/cm2. Cu and Cr co-doping promoted electron transfer to surface Ni active centers, significantly increasing surface electron density and optimizing the adsorption-desorption kinetics of hydrogen intermediates. The NiCu0.05Cr0.02/CA-U catalyst obtained through CA-U morphology regulation showed good OER performance, with an overpotential of 348 mV at 10 mA/cm2, outperforming the Ru-containing reference catalyst Ru0.03NiCu0.05Cr0.02/CA-U. [Conclusion] A multicomponent and morphologyregulating strategy was used to prepare NiCuCr ternary alloy catalysts and regulate their surface electronic structure. The materials exhibited good HER and OER performance, providing a new idea for developing low-cost, high-efficiency bifunctional Ni-based electrocatalysts.
[1] Turner J A. Sustainable hydrogen production[J]. Science, 2004, 305(5686):972-974.
[2] Chu S, Majumdar A. Opportunities and challenges for a sustainable energy future[J]. Nature, 2012, 488(7411):294-303.
[3] Seh Z W, Kibsgaard J, Dickens C F, et al. Combining theory and experiment in electrocatalysis:Insights into materials design[J].Science, 2017, 355(6321):eaad4998.
[4] Chatenet M, Pollet B G, Dekel D R, et al. Water electrolysis:from textbook knowledge to the latest scientific strategies and industrial developments[J]. Chemical Society Reviews, 2022, 51(11):4583-4762.
[5] You B, Sun Y J. Innovative strategies for electrocatalytic water splitting[J]. Accounts of Chemical Research, 2018, 51(7):1571-1580.
[6] Danilovic N, Subbaraman R, Strmcnik D, et al. Enhancing the alkaline hydrogen evolution reaction activity through the bifunctionality of Ni(OH)2/metal catalysts[J]. Angewandte Chemie International Edition, 2012, 51(50):12495-12498.
[7] Mc Crory C C L, Jung S, Peters J C, et al. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction[J].Journal of the American Chemical Society, 2013, 135(45):16977-16987.
[8] Ali A, Shen P K, Idrees F, et al. Recent progress in graphenebased nanostructured electrocatalysts for overall water splitting[J].Electrochemical Energy Reviews, 2020, 3(2):370-394.
[9] Zou X X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting[J]. Chemical Society Reviews, 2015, 44(15):5148-5180.
[10] Roger I, Shipman M A, Symes M D. Earth-abundant catalysts for electrochemical and photoelectrochemical water splitting[J]. Nature Reviews Chemistry, 2017, 1(1):0003.
[11] Gong M, Li Y G, Wang H L, et al. An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation[J]. Journal of the American Chemical Society, 2013, 135(23):8452-8455.
[12]石鑫婷,邢乐红,孟凡旭,等.镍基TiO2复合电极的制备及电催化析氢性能[J].电镀与涂饰, 2023, 42(8):34-40.Shi X T, Xing L H, Meng F X, et al. Preparation of Ni-based TiO2composite electrode and its electrocatalytic activity for hydrogen evolution reaction[J]. Electroplating&Finishing, 2023, 42(8):34-40.
[13]张行,卓煜,陈蔼峻,等.镍钴磷化物/泡沫镍电解水制氢膜电极的制备及性能[J].电镀与涂饰, 2026, 45(1):115-122.Zhang H, Zhuo Y, Chen A J, et al. A NiCoP/nickel foam composite membrane electrode for hydrogen production via water electrolysis:preparation and properties[J]. Electroplating&Finishing, 2026, 45(1):115-122.
[14] Gao Y J, Yu J L, Lu M Y, et al. Optimizing nickel-based electrocatalysts for hydrogen and oxygen evolution:electronic and geometric perspectives[J]. Small Methods, 2025, 9(11):e01036.
[15] Greeley J, Jaramillo T F, Bonde J, et al. Computational highthroughput screening of electrocatalytic materials for hydrogen evolution[J]. Nature Materials, 2006, 5(11):909-913.
[16] Zhang J Q, Zhao Y F, Guo X, et al. Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction[J]. Nature Catalysis, 2018, 1(12):985-992.
[17] Yang P Z, Long Y H, Huang W L, Liu D F, et al. Single-atom copper embedded in two-dimensional MXene toward peroxymonosulfate activation to generate singlet oxygen with nearly 100%selectivity for enhanced Fenton-like reactions[J]. Applied Catalysis B:Environmental, 2022, 310:122245.
[18] Alam M K, Mohanta M K, White D, et al. Facile synthesis of cubic Ni₁-x Crx nanoalloys and their composition-dependent electrocatalytic activity for the hydrogen evolution reaction[J]. Nanotechnology, 2025, 36(22):225401.
[19] Wang X D, Liu X R, Fang J J, et al. Tuning the apparent hydrogen binding energy to achieve high-performance Ni-based hydrogen oxidation reaction catalyst[J]. Nature Communications, 2024, 15(1):1137.
[20] Lei C J, Yu W, Hou Y, et al. Efficient alkaline hydrogen evolution on atomically dispersed Ni–Nx Species anchored porous carbon with embedded Ni nanoparticles by accelerating water dissociation kinetics[J].Energy&Environmental Science, 2019, 12(1):149-156.
[21] Chen Z J, Duan X G, Wei W, et al. Recent advances in transition metal-based electrocatalysts for alkaline hydrogen evolution[J].Journal of Materials Chemistry A, 2019, 7(25):14971-15005.
[22] Sun Y Y, Ganin A Y. The synergistic effects of alloying on the performance and stability of Co3Mo and Co7Mo6 for the electrocatalytic hydrogen evolution reaction[J]. Hydrogen, 2020, 1(1):11-21.
[23] Yang M, Liu F, Gan J, et al. Insight into regulating effect of citric acid on Ni-Cr catalysts for enhanced urea electro-oxidation[J]. Molecular Catalysis, 2026, 588:115551.
[24]张立娟.镍基催化剂二氧化碳甲烷化反应性能研究[D].天津:天津大学, 2018.Zhang L J. Carbon dioxide methanation performance on Ni-based catalyst[D]. Tianjin:Tianjin University, 2018.
[25]康伟伟,吴旭,成强强,等.类水滑石基Ni CuFe催化剂的制备及其在乙醇水蒸气重整制氢的应用[J].天然气化工, 2018, 43(5):43-48, 110.Kang W W, Wu X, Cheng Q Q, et al. Preparation of hydrotalcite based NiCuFe catalyst for hydrogen production by steam reforming of ethanol[J]. Natural Gas Chemical Industry, 2018, 43(5):43-48, 110.
[26] Zou J C, Song G Y, Cui A G, et al. Multiple strategies regulating the d-band center of Ni2P/NiFe2O4@N-GTs hierarchical nanoarchitecture as efficient electrocatalyst for overall water splitting[J].International Journal of Hydrogen Energy, 2024, 80:91-103.
[27] Liu S H, Shi Y F, Tang F Q, et al. Cr dopant regulating d-orbital electronic configuration of NiFe spinel oxide to improve oxygen evolution reaction in Zn-air battery[J]. Journal of Alloys and Compounds, 2024, 987:174248.
[28] Vegard L. Die Konstitution der Mischkristalle und die Raumfüllung der Atome[J]. Zeitschrift für Physik, 1921, 5(1):17-26.
[29] Cottrell A H, Dexter D L. Dislocations and plastic flow in crystals[J].American Journal of Physics, 1954, 22(4):242-243.
[30] Cahn J W. The impurity-drag effect in grain boundary motion[J].Acta Metallurgica, 1962, 10(9):789-798.
[31] Hu G W, Zeng L C, Du H, et al. Combined effects of solute drag and Zener pinning on grain growth of a NiCoCr medium-entropy alloy[J].Intermetallics, 2021, 136:107271.
[32] Ungár T. Microstructural parameters from X-ray diffraction peak broadening[J]. Scripta Materialia, 2004, 51(8):777-781.
基本信息:
DOI：10.19289/j.1004-227x.2026.09.001
中图分类号:TQ116.2;O643.36
引用信息:
[1]陈远媚,洪荣富,杜磊,等.镍基三元合金表面协同电子结构调制及其析氢和析氧性能[J].电镀与涂饰,2026,45(09):1-9.DOI:10.19289/j.1004-227x.2026.09.001.
基金信息:
国家自然科学基金（22250710133）
2026-05-07
2026
2026-09-23
2026-07-13
2026
1
2026-06-05
2026-06-05
2026-06-05