等离子体辅助制备N掺杂NiMo合金助力高效碱性水氧化

doi:10.11949/0438-1157.20251002

摘要/Abstract

摘要：

电解水制氢是实现能源结构调整与优化的最具潜力绿色制氢技术，阳极析氧反应（OER）缓慢的四电子转移过程是限制整体效率的重要原因。因此，高效稳定OER催化剂的开发对电解水实际应用意义重大。本文采用成本低廉、绿色高效的氮气等离子体技术制备了氮（N）掺杂NiMo合金催化剂（N-NiMo），展现了优异的OER性能。N以原子的形式掺杂在NiMo合金晶格中且引发了晶格压缩应变，有效调控了NiMo合金的电子结构，该催化剂在100 mA/cm²的电流密度下过电位低至230 mV （1.0 M KOH）。在模拟碱化海水（1.0 M KOH + 0.5 M NaCl）和碱化真实海水（1.0 M KOH + 海水）中，N-NiMo仍具有较好的催化活性（η₁₀₀=265 mV， η₁₀₀=266 mV）。此外，在500 mA/cm²工业电流密度下，该催化剂在碱水和碱化真实海水中可持续工作1000 h，表现出优异稳定性。最后，使用N-NiMo作为阳极构建了阴离子交换膜电解槽，在碱化真实海水中，该电解槽仅在1.77 V的低电压下即可达到1000 mA/cm²的电流密度，展现出实际应用的巨大潜力。

关键词: 电化学, 析氧反应, 催化剂, 等离子体, 海水电解

Abstract:

Water electrolysis stands as the most promising green hydrogen production technology for energy structure adjustment and optimization. The sluggish four-electron transfer process of the anodic oxygen evolution reaction (OER) significantly limits overall electrolysis efficiency, making the development of highly efficient and stable OER catalysts critical for practical applications. In this study, a cost-effective and environmentally benign nitrogen plasma technique was employed to fabricate a N-doped NiMo alloy catalyst (N-NiMo). Nitrogen (N) atoms were successfully doped into the NiMo alloy lattice, inducing compressive lattice strain. Benefiting from optimized electronic structures, N-NiMo demonstrates exceptional OER performance with an ultralow overpotential of 230 mV at 100 mA/cm² in 1.0 M KOH. In simulated alkalized seawater (1.0 M KOH + 0.5 M NaCl) and real alkalized seawater (1.0 M KOH + seawater) electrolytes, N-NiMo retained remarkable catalytic activity (η₁₀₀=265 mV, η₁₀₀=266 mV). Furthermore, under industrial-scale current density (500 mA/cm²), the catalyst demonstrated exceptional stability with continuous operation for 1000 h in both alkalized water and real alkalized seawater environments. Finally, an anion exchange membrane electrolyzer incorporating the N-NiMo as the anode achieved an industrial-grade current density of 1000 mA/cm² at ultralow cell voltages of 1.77 V in real alkalized seawater electrolytes, demonstrating significant potential for practical implementation.

Key words: electrochemistry, oxygen evolution reaction, catalyst, plasma, seawater electrolysis

中图分类号:

TQ 116.2

王艳皎, 王旻, 吴明铂, 胡涵. 等离子体辅助制备N掺杂NiMo合金助力高效碱性水氧化[J]. 化工学报, DOI: 10.11949/0438-1157.20251002.

Yanjiao WANG, Min WANG, Mingbo WU, Han HU. Plasma-prepared N-doped NiMo alloy boosts efficient alkaline water oxidation[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251002.

图/表 6

图1 氮气等离子体制备N-NiMo用于碱性OER (a)，氮气等离子体射频功率 (b) 和处理时间 (c) 对催化剂OER性能的影响探究

Fig.1 Schematic illustration of N-NiMo fabrication via nitrogen plasma technology for alkaline oxygen evolution reaction (a), correlation between RF power of nitrogen plasma and OER catalytic activity (b), correlation between treatment time of nitrogen plasma and OER catalytic activity (c)

图2 NiMo和N-NiMo的XRD全谱图 (a)，XRD局部放大谱图 (b)，Ni 2p高分辨XPS谱图 (c)， Mo 3d高分辨XPS谱图 (d)，FT-EXAFS谱图 (e)，和XANES谱图 (f)

Fig. 2 Full-range XRD pattern (a), high-resolution XRD pattern (b), high-resolution XPS spectra of Ni 2p (c), high-resolution XPS spectra of Mo 3d (d), FT-EXAFS pattern (e) and XANES pattern (f) of NiMo and N-NiMo

图3 NiMo合金 (a) 和N-NiMo (b) 的扫描电子显微镜图像，NiMo合金和N-NiMo的水接触角图像 (c)，N-NiMo的高分辨率透射电子显微镜图像 (d)，N-NiMo的高角度环形暗场扫描透射电子显微镜图像及其对应的元素分布图 (e)

Fig.3 SEM images of NiMo alloy (a) and N-NiMo (b), water contact angle image of NiMo alloy and N-NiMo (c), HRTEM image of N-NiMo (d), HAADF-STEM image and corresponding elemental mapping of N-NiMo (e)

图4 NiMo合金 (a) 和N-NiMo (b) 的晶格应变分布图像

Fig.4 The lattice strain distribution images of NiMo alloy (a) and N-NiMo (b)

图5 N-NiMo在碱水中的LSV极化曲线 (a)，Tafel斜率图 (b)，奈奎斯特阻抗图 (c)，电容Cdl图 (d)，N-NiMo在不同电解质中的LSV极化曲线图 (e)，N-NiMo在碱水和碱化真实海水中的稳定性测试图 (f)

Fig.5 The LSV polarization curve of N-NiMo in alkalized water (a), Tafel slope diagram (b), Nyquist impedance diagram (c), capacitance Cdl diagram (d), LSV polarization curve diagram of N-NiMo in different electrolytes (e), stability test diagram of N-NiMo in alkalized water and alkalized real seawater (f)

图6 Pt/C||N-NiMo阴离子交换膜电解槽的极化曲线 (a)，电解槽在1.5 V电压下的奈奎斯特图 (b)，电解槽在碱化真实海水中的稳定性测试图 (c)

Fig.6 The polarization curve of the Pt/C||N-NiMo anion exchange membrane electrolyzer (a), Nyquist diagram of the electrolyzer at the voltage of 1.5 V (b), stability test diagram of the electrolyzer in alkalized real seawater (c)

参考文献 33

[1]	黄晟, 杨振丽, 李振宇. 氢产业链发展的路径分析[J]. 化工进展, 2024, 43(2): 882-893.
	Huang S, Yang Z L, Li Z Y. Analysis of optimization path of developing China's hydrogen industry[J]. Chemical Industry and Engineering Progress, 2024, 43(2): 882-893.
[2]	张真, 张凡, 云祉婷. 绿氢在石化和化工行业的减碳经济性分析[J]. 化工进展, 2024, 43(6): 3021-3028.
	Zhang Z, Zhang F, Yun Z T. Carbon reduction and techno-economic analysis of using green hydrogen in chemical and petrochemical industry[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3021-3028.
[3]	Wan L, Xu Z A, Xu Q, et al. Key components and design strategy of the membrane electrode assembly for alkaline water electrolysis[J]. Energy & Environmental Science, 2023, 16(4): 1384-1430.
[4]	Zainal B S, Ker P J, Mohamed H, et al. Recent advancement and assessment of green hydrogen production technologies[J]. Renewable and Sustainable Energy Reviews, 2024, 189: 113941.
[5]	张生安, 刘桂莲. 高效太阳能电解水制氢系统及其性能的多目标优化[J]. 化工学报, 2023, 74(3): 1260-1274.
	Zhang S A, Liu G L. Multi-objective optimization of high-efficiency solar water electrolysis hydrogen production system and its performance[J]. CIESC Journal, 2023, 74(3): 1260-1274.
[6]	Liu Y, Wang Y, Fornasiero P, et al. Long-term durability of seawater electrolysis for hydrogen: from catalysts to systems[J]. Angewandte Chemie International Edition, 2024, 63(47): e202412087.
[7]	Wang Y J, Wang M, Yang Y Q, et al. Potential technology for seawater electrolysis: Anion-exchange membrane water electrolysis[J]. Chem Catalysis, 2023, 3(7): 100643.
[8]	Liu D, Cai Y H, Wang X, et al. Innovations in electrocatalysts, hybrid anodic oxidation, and electrolyzers for enhanced direct seawater electrolysis[J]. Energy & Environmental Science, 2024, 17(19): 6897-6942.
[9]	Meskher H, Woldu A R, Chu P K, et al. Sustainability assessment of seawater splitting: Prospects, challenges, and future directions[J]. EcoEnergy, 2024, 2(4): 630-651.
[10]	Gong S M, Meng Y, Jin Z Y, et al. Recent progress on the stability of electrocatalysts under high current densities toward industrial water splitting[J]. ACS Catalysis, 2024, 14(19): 14399-14435.
[11]	赵娟, 吴梦成, 雷惊雷, 等. 一步水热法制备电解水析氧反应Ni₃S₂@Mo₂S₃高效催化剂[J]. 化工学报, 2022, 73(4): 1575-1584.
	Zhao J, Wu M C, Lei J L, et al. One-step hydrothermal method toward preparation of Ni₃S₂@Mo₂S₃ high-efficient catalyst for oxygen evolution reaction in water electrolysis[J]. CIESC Journal, 2022, 73(4): 1575-1584.
[12]	郑学文, 赵蕊, 吴家哲, 等. 电解海水催化剂的设计与改性[J]. 化工进展, 2022, 41(11): 5800-5810.
	Zheng X W, Zhao R, Wu J Z, et al. Design and modification of electrocatalysts for seawater splitting: a review[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 5800-5810.
[13]	Quan L, Jiang H, Mei G L, et al. Bifunctional electrocatalysts for overall and hybrid water splitting[J]. Chemical Reviews, 2024, 124(7): 3694-3812.
[14]	柴亚婷,路家伟,王蕊欣,等碳纸自支撑N掺杂碳纳米管复合MoC/NiCo异质结构的电解水析氧性能 [J]. 化工学报, 2023, 74(12): 4904-4913.
	Chai Y T, Lu J W, Wang R X, et al. Carbon paper self-supported N-doped carbon nanotubes with MoC/NiCo heterostructures for electrolytic water oxygen evolution reactio[J]. CIESC Journal, 2023, 74(12): 4904-4913.
[15]	Wang Y J, Wang M, Wang B, et al. Ultrafast reconstruction of Ni-based alloy precatalyst for robust seawater oxidation[J]. Advanced Functional Materials, 2025, 35(44): 2509590.
[16]	Du W, Shi Y M, Zhou W, et al. Unveiling the in situ dissolution and polymerization of Mo in Ni₄Mo alloy for promoting the hydrogen evolution reaction[J]. Angewandte Chemie International Edition, 2021, 60(13): 7051-7055.
[17]	Kang X, Yang F N, Zhang Z Y, et al. A corrosion-resistant RuMoNi catalyst for efficient and long-lasting seawater oxidation and anion exchange membrane electrolyzer[J]. Nature Communications, 2023, 14: 3607.
[18]	Liu D, Wei X T, Lu J X, et al. Efficient and ultrastable seawater electrolysis at industrial current density with strong metal-support interaction and dual Cl--repelling layers[J]. Advanced Materials, 2024, 36(49): 2408982.
[19]	Shao L, Han X D, Shi L, et al. In situ generation of molybdate-modulated nickel-iron oxide electrodes with high corrosion resistance for efficient seawater electrolysis[J]. Advanced Energy Materials, 2024, 14(4): 2303261.
[20]	Xiao L Y, Yang T T, Cheng C Q, et al. Coupled compressive-tensile stains boosting both activity and durability of NiMo electrode for alkaline water/seawater hydrogen evolution at high current densities[J]. Chemical Engineering Journal, 2024, 485: 150044.
[21]	Zou X X, Zhao X Y, Pang B H, et al. Interstitial oxygen acts as electronic buffer stabilizing high-entropy alloys for trifunctional electrocatalysis[J]. Advanced Materials, 2024, 36(50): 2412954.
[22]	Fan H F, Chen W, Chen G L, et al. Plasma-heteroatom-doped Ni-V-Fe trimetallic phospho-nitride as high-performance bifunctional electrocatalyst[J]. Applied Catalysis B: Environment and Energy, 2020, 268: 118440.
[23]	Li Y W, Wang M G, Tian J F, et al. Nitrogen-metal-oxygen moieties enriched surface reconstruction in CoFe electrocatalysts for stabilizing high-valence Co sites enable water oxidation[J]. Applied Surface Science, 2024, 669: 160588.
[24]	Zhang S Y, Ruan W D, Guan J Q. Strain effects in carbon dioxide electroreduction[J]. Advanced Energy Materials, 2025, 15(14): 2404057.
[25]	Zhang H M, Chi K B, Qiao L, et al. Boosting acidic hydrogen evolution kinetics induced by weak strain effect in PdPt alloy for proton exchange membrane water electrolyzers[J]. Small, 2024, 20(51): 2406935.
[26]	Zhu C H, Xu L J, Liu M J, et al. A review on improving mechanical properties of high entropy alloy: interstitial atom doping[J]. Journal of Materials Research and Technology, 2023, 24: 7832-7851.
[27]	Jiang W T, Li R D, He J Y, et al. Nitrogen-doping assisted local chemical heterogeneity and mechanical properties in CoCrMoW alloys manufactured via laser powder bed fusion[J]. Advanced Powder Materials, 2024, 3(5): 100217.
[28]	Wang S, Yuan C Z, Zheng Y S, et al. Boosting the bifunctionality and durability of cobalt-fluoride-oxide nanosheets for alkaline water splitting through nitrogen-plasma-promoted electronic regulation and structural reconstruction[J]. ACS Catalysis, 2024, 14(5): 3616-3626.
[29]	Jin R X, Huang J, Chen G L, et al. Water-sprouted, plasma-enhanced Ni-Co phospho-nitride nanosheets boost electrocatalytic hydrogen and oxygen evolution[J]. Chemical Engineering Journal, 2020, 402: 126257.
[30]	Patil R B, House S D, Mantri A, et al. Direct observation of Ni–Mo bimetallic catalyst formation via thermal reduction of nickel molybdate nanorods[J]. ACS Catalysis, 2020, 10(18): 10390-10398.
[31]	Chen K, Kim S, Rajendiran R, et al. Enhancing ORR/OER active sites through lattice distortion of Fe-enriched FeNi₃ intermetallic nanoparticles doped N-doped carbon for high-performance rechargeable Zn-air battery[J]. Journal of Colloid and Interface Science, 2021, 582: 977-990.
[32]	Zhao Z, Qin S Y, Li X, et al. Sulfur-facilitated in situ deep reconstruction of transition metal molybdates toward superior electrocatalytic oxidation of alkaline seawater[J]. Chem Catalysis, 2024, 4(11): 101144.
[33]	Hao W J, Ma X W, Wang L C, et al. Surface corrosion-resistant and multi-scenario MoNiP electrode for efficient industrial-scale seawater splitting[J]. Advanced Energy Materials, 2025, 15(5): 2403009.