FeNi3-Fe3O4/CN催化剂的制备及其电催化析氧性能

doi:10.16085/j.issn.1000-6613.2024-0966

摘要/Abstract

摘要：

电解水制氢中的阳极析氧反应（OER）因反应能垒较高，降低了电解水的效率，因此研发高效的析氧催化剂是推动电解水产业化的重要途径。本文通过高温热解聚苯胺、硝酸铁和硝酸镍制备了一系列不同Fe和Ni含量的FeNi/CN催化剂。通过X射线衍射（XRD）、透射电镜（TEM）和X射线光电子能谱（XPS）等分析手段表征了催化剂的结构，采用线性扫描伏安法（LSV）和计时电位法（CP）等方法在碱性电解液中评价了催化剂的电化学析氧性能。结果表明，所制备的催化剂中含有FeNi₃和Fe₃O₄纳米颗粒，这些颗粒很好地分散在聚苯胺衍生的碳上。随着铁含量的逐渐降低，OER过电位表现出先减小后增大的趋势。其中，Fe1Ni1/CN催化剂具有最低的OER过电位，在10mA/cm²下的过电位仅为339mV，Tafel斜率为87mV/dec，表现出最好的OER催化活性，优于文献中报道的大多数铁基和镍基催化剂。

关键词: 电化学, 催化剂, 复合材料, 析氧反应, 四氧化三铁, 镍铁合金

Abstract:

In water electrolysis to hydrogen, the oxygen evolution reaction (OER) on the anode has a high energy barrier, which reduces the efficiency of water electrolysis. Therefore, the development of efficient oxygen evolution catalysts is crucial to promote the industrialization of water electrolysis. A series of FeNi/CN catalysts with various Fe and Ni contents were prepared by high-temperature pyrolysis of polyaniline, ferric nitrate and nickel nitrate. The structure of the catalysts was characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), and their electrochemical OER performance in alkaline electrolyte was evaluated using linear sweep voltammetry (LSV) and chronoamperometry (CP). The results showed that the prepared catalysts containing FeNi₃ and Fe₃O₄ nanoparticles were well-dispersed on the polyaniline-derived carbon. With the gradual decrease in Fe content, the OER overpotential initially decreased and then increased. The Fe1Ni1/CN catalyst exhibited the lowest OER overpotential of only 339mV at 10mA/cm² and a Tafel slope of 87mV/dec, demonstrating an OER activity superior to most iron-based and nickel-based catalysts reported in the literature.

Key words: electrochemistry, catalyst, composites, oxygen evolution reaction, ferroferric oxide (Fe₃O₄), NiFe alloy

中图分类号:

TQ138.1

陈东健, 孙雨倩, 银凤翔. FeNi₃-Fe₃O₄/CN催化剂的制备及其电催化析氧性能[J]. 化工进展, 2025, 44(7): 3928-3937.

CHEN Dongjian, SUN Yuqian, YIN Fengxiang. Preparation of FeNi₃-Fe₃O₄/CN electrocatalysts and their electrocatalytic oxygen evolution performance[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 3928-3937.

图/表 10

图1 FeNi/CN系列催化剂制备流程

图2 Fe1.3Ni0.7/CN、Fe1Ni1/CN、Fe0.7Ni1.3/CN的XRD谱图和FTIR谱图

图3 Fe1Ni1/CN的TEM图

图4 Fe1Ni1/CN的XPS谱图

图5 Fe1Ni1/CN催化剂表面元素含量扇形统计图

图6 Fe1Ni1/CN催化剂与Fe/CN、Ni/CN催化剂的OER性能对比

图7 FeNi/CN系列催化剂的OER性能曲线对比

表1 铁基和镍基催化剂的OER过电位和Tafel斜率

催化剂	电解液	η₁₀/mV	Tafel斜率/mV·dec^-1	参考文献
Fe1Ni1/CN	1mol/L KOH	339	87	本工作
Fe₃O₄/FeS₂	1mol/L KOH	253	48	[14]
FeNi₃N-Ni₃S₂	1mol/L KOH	230	39	[24]
FeNiO _x /C	1mol/L KOH	310	58	[36]
Fe₃O₄@N-HCNT	1mol/L KOH	500	64	[37]
Fe-NiO	1mol/L KOH	380	42	[38]
Ni₃FeN	0.1mol/L KOH	355	70	[39]
NiFe-LDH/CNT	0.1mol/L KOH	350	54	[40]
NiFe₂O _x	1mol/L KOH	356	57	[41]
Ni₉S₈	1mol/L KOH	480	56	[42]
Fe _x Ni_1-_x Co₂O₄	1mol/L KOH	350	27	[43]

图8 Fe1Ni1/CN的CV图和FeNi/CN催化剂的Cdl图和EIS奈奎斯特图

图9 Fe1Ni1/CN催化剂的原位FTIR光谱图

参考文献 50

[1]	梁严, 吴璇, 王军, 等. “双碳”背景下天然气制氢先进技术及应用场景[J]. 当代化工研究, 2023(16): 101-103.
	LIANG Yan, WU Xuan, WANG Jun, et al. Advanced technology and application scenarios of natural gas to hydrogen in the context of carbon peaking and carbon neutrality[J]. Modern Chemical Research, 2023(16): 101-103.
[2]	我国首个甲醇制氢加氢一体站投用[J]. 中国环境监察, 2023(S1): 5.
	China’s first integrated methanol hydrogen production and hydrogenation station put into use[J]. China Environment Supervision, 2023(S1): 5.
[3]	解寅珑, 云红红, 白韡, 等. 电解水制氢气用催化剂制备及应用性能[J]. 化学工程师, 2023, 37(8): 106-111.
	XIE Yinlong, YUN Honghong, BAI Wei, et al. Preparation and application performance of catalyst for hydrogen production from electrolytic water[J]. Chemical Engineer, 2023, 37(8): 106-111.
[4]	CHENG Guishi, YANG Yihao, XIU Taichun, et al. Analysis of hydrogen production potential from water electrolysis in China[J]. Energy & Fuels, 2023, 37(13): 9220-9232.
[5]	YAO Dongxue, GU Lingling, ZUO Bin, et al. A strategy for preparing high-efficiency and economical catalytic electrodes toward overall water splitting[J]. Nanoscale, 2021, 13(24): 10624-10648.
[6]	符淑瑢, 王丽娜, 王东伟, 等. 析氧助催化剂增强光阳极光电催化分解水性能研究进展[J]. 化工进展, 2023, 42(5): 2353-2370.
	FU Shurong, WANG Lina, WANG Dongwei, et al. Oxygen evolution cocatalyst enhancing the photoanode performances for photoelectrochemical water splitting[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2353-2370.
[7]	胡志豪, 张皓景, 周叶, 等. 高效镍基有序多孔电极气泡行为可视化观测及性能影响[J]. 化工进展, 2024, 43(2): 680-687.
	HU Zhihao, ZHANG Haojing, ZHOU Ye, et al. Visualization observation of bubble behavior and performance impact analysis in efficient nickel based ordered porous electrodes[J]. Chemical Industry and Engineering Progress, 2024, 43(2): 680-687.
[8]	ZHU Mengshu, AI Xiaomeng, FANG Jiakun, et al. Optimal integration of electrolysis, gasification and reforming for stable hydrogen production[J]. Energy Conversion and Management, 2023, 292: 117400.
[9]	田锦锐, 田浩, 戴佳玮, 等. 自支撑电极电解水制氢应用研究进展[J]. 化学试剂, 2023, 45(6): 78-87.
	TIAN Jinrui, TIAN Hao, DAI Jiawei, et al. Progress of hydrogen production application by water electrolysis with self-supported electrode[J]. Chemical Reagents, 2023, 45(6): 78-87.
[10]	张静, 贺业亨, 王晶晶, 等. 电沉积法制备碱性电解水镍基析氧电极的研究进展[J]. 化工进展, 2023, 42(12): 6239-6250.
	ZHANG Jing, HE Yeheng, WANG Jingjing, et al. Research progress on nickel-based oxygen evolution electrode prepared by electrodeposition for alkaline water electrolysis[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6239-6250.
[11]	JAMESH Mohammed-Ibrahim, SUN Xiaoming. Recent progress on earth abundant electrocatalysts for oxygen evolution reaction (OER) in alkaline medium to achieve efficient water splitting—A review[J]. Journal of Power Sources, 2018, 400: 31-68.
[12]	TAMILARASI B, JITHUL K P, PANDEY J. Non-noble metal-based electro-catalyst for the oxygen evolution reaction (OER): Towards an active & stable electro-catalyst for PEM water electrolysis[J]. International Journal of Hydrogen Energy, 2024, 58: 556-582.
[13]	WU Zhipeng, LU Xuefeng, ZANG Shuangquan, et al. Non-noble-metal-based electrocatalysts toward the oxygen evolution reaction[J]. Advanced Functional Materials, 2020, 30(15): 1910274.
[14]	MALEK Abdul, XUE Yanrong, LU Xu. Dynamically restructuring Ni _x Cr _y O electrocatalyst for stable oxygen evolution reaction in real seawater[J]. Angewandte Chemie International Edition, 2023, 62(40): e202309854.
[15]	CHEN Qiao, USMAN Zahid, WEI Jie, et al. Efficient O-O coupling at catalytic interface to assist kinetics optimization on concerted and sequential proton-electron transfer for water oxidation[J]. ACS Nano, 2023, 17(13): 12278-12289.
[16]	GONG Lanqian, YANG Huan, DOUKA Abdoulkader Ibro, et al. Recent progress on NiFe-based electrocatalysts for alkaline oxygen evolution[J]. Advanced Sustainable Systems, 2021, 5(1): 2000136.
[17]	DENG Chen, WU Kuang-Hsu, SCOTT Jason, et al. Core/shell NiFe nanoalloy with a discrete N-doped graphitic carbon cover for enhanced water oxidation[J]. ChemElectroChem, 2018, 5(5): 732-736.
[18]	韩银凤, 张瑞林. 以泡沫镍为基底的纳米片层状Ni²⁺-Fe³⁺-V³⁺-LDHs的制备及其电催化析氧性能研究[J]. 化学试剂, 2020, 42(1): 8-12.
	HAN Yinfeng, ZHANG Ruilin. Preparation and electrolytic oxygen evolution performance characteration of Ni²⁺-Fe³⁺-V³⁺ LDHs with nanosheet structure based on foam nickel[J]. Chemical Reagents, 2020, 42(1): 8-12.
[19]	ZHENG Dong, YU Linhai, LIU Wenxian, et al. Structural advantages and enhancement strategies of heterostructure water-splitting electrocatalysts[J]. Cell Reports Physical Science, 2021, 2(6): 100443.
[20]	MA Hancheng, DING Yao, LI Jianqi, et al. Approaching high oxygen evolution reaction performance by synergetic dual-ion leaching[J]. Nano Research, 2024, 17(9): 7975-7983.
[21]	LI Yichuan, TANG Guoqiang, WANG Yu, et al. Interfacial engineering of a phase-controlled heterojunction for high-efficiency HER, OER, and ORR trifunctional electrocatalysis[J]. ACS Omega, 2022, 7(16): 13687-13696.
[22]	PAN Jiaqi, CHEN Zhanfen, WANG Panhong, et al. The overall water splitting of CdS/Ti³⁺-SrTiO₃ core-shell heterojunction via OER enhancement of MnO _x nanoparticles[J]. Chemical Engineering Journal, 2021, 424: 130357.
[23]	PAN Jiaqi, WANG Panhong, WANG Peipei, et al. The photocatalytic overall water splitting hydrogen production of g-C₃N₄/CdS hollow core-shell heterojunction via the HER/OER matching of Pt/MnO _x [J]. Chemical Engineering Journal, 2021, 405: 126622.
[24]	WU Dongting, KONG Aiqun, LI Wei, et al. Facile synthesis of bimetallic Ni-Fe phosphide as robust electrocatalyst for oxygen evolution reaction in alkaline media[J]. International Journal of Hydrogen Energy, 2021, 46(80): 39844-39854.
[25]	WANG Minjie, ZHENG Xingqun, SONG Lele, et al. Fe₃O₄/FeS₂ heterostructures enable efficient oxygen evolution reaction[J]. Journal of Materials Chemistry A, 2020, 8(28): 14145-14151.
[26]	LIANG Shuqin, JING Meizan, PERVAIZ Erum, et al. Nickel-iron nitride-nickel sulfide composites for oxygen evolution electrocatalysis[J]. ACS Applied Materials & Interfaces, 2020, 12(37): 41464-41470.
[27]	BANJAR Mohd Faizar, ABEDIN Fatin Najwa Joynal, FIZAL Ahmad Noor Syimir, et al. Synthesis and characterization of a novel nanosized polyaniline[J]. Polymers, 2023, 15(23): 4565.
[28]	WANG Jie, ZHAO Shuo, WANG Jin, et al. In-situ embedding Co₉S₈ nanoparticles in polyaniline-based carbon nanotubes for enhanced lithium storage[J]. Journal of Alloys and Compounds, 2022, 919: 165819.
[29]	FENG Juan, ZONG Yan, SUN Yong, et al. Optimization of porous FeNi₃/N-GN composites with superior microwave absorption performance[J]. Chemical Engineering Journal, 2018, 345: 441-451.
[30]	HAN Cong’ai, ZHANG Haiyan, ZHANG Danfeng, et al. Ultrafine FeNi₃ nanocrystals embedded in 3D honeycomb-like carbon matrix for high-performance microwave absorption[J]. Nanomaterials, 2020, 10(4): 598.
[31]	WANG Lili, LI Na, ZHAO Tiqi, et al. Magnetic properties of FeNi₃ nanoparticle modified Pinus radiata wood nanocomposites[J]. Polymers, 2019, 11(3): 421.
[32]	GAO Qiuyue, LI Guoru, KOFIE Gideon, et al. Ionic liquid/ZIF-67 derived Co₉S₈-SNC catalyst for oxygen reduction reaction in alkaline electrolyte[J]. Carbon Letters, 2024, 34(3): 951-960.
[33]	LIU Yang, ZHANG Shiqing, MA Shaokai, et al. Electronic structure modification of MnO₂ nanosheet arrays with enhanced water oxidation activity and stability by nitrogen plasma[J]. ACS Applied Materials & Interfaces, 2024, 16(28): 36498-36508.
[34]	ZHENG Lingxia, YE Weiqing, ZHAO Yijian, et al. Defect-induced atomic arrangement in CoFe bimetallic heterostructures with boosted oxygen evolution activity[J]. Small, 2023, 19(9): 2205092.
[35]	SUEN Nian-Tzu, HUNG Sung-Fu, QUAN Quan, et al. Electrocatalysis for the oxygen evolution reaction: Recent development and future perspectives[J]. Chemical Society Reviews, 2017, 46(2): 337-365.
[36]	CHEN Hui, HUANG Xiaoxi, ZHOU Lijing, et al. Electrospinning synthesis of bimetallic nickel-iron oxide/carbon composite nanofibers for efficient water oxidation electrocatalysis[J]. ChemCatChem, 2016, 8(5): 992-1000.
[37]	SHI Kun, ZHENG Man, LIU Jiaxian, et al. Novel Fe₃O₄ nanoparticles encapsulated in and loaded on hollow carbon nanotubes wrapped dendritic carbon layers architecture for water decomposition[J]. International Journal of Hydrogen Energy, 2024, 51: 1303-1317.
[38]	KIM Sang Jun, Seung Geun JO, LEE Eún Been, et al. Morphology-controlled nickel oxide and iron-nickel oxide for electrochemical oxygen evolution reaction[J]. ACS Applied Energy Materials, 2023, 6(16): 8360-8367.
[39]	FU Gengtao, CUI Zhiming, CHEN Yifan, et al. Hierarchically mesoporous nickel-iron nitride as a cost-efficient and highly durable electrocatalyst for Zn-air battery[J]. Nano Energy, 2017, 39: 77-85.
[40]	GONG Ming, LI Yanguang, WANG Hailiang, 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.
[41]	CHERVIN Christopher N, DESARIO Paul A, PARKER Joseph F, et al. Aerogel architectures boost oxygen-evolution performance of NiFe₂O _x spinels to activity levels commensurate with nickel-rich oxides[J]. ChemElectroChem, 2016, 3(9): 1369-1375.
[42]	LI Hao, SHAO Youdong, SU Yantao, et al. Vapor-phase atomic layer deposition of nickel sulfide and its application for efficient oxygen-evolution electrocatalysis[J]. Chemistry of Materials, 2016, 28(4): 1155-1164.
[43]	YAN Kaili, SHANG Xiao, LI Zhen, et al. Ternary mixed metal Fe-doped NiCo₂O₄ nanowires as efficient electrocatalysts for oxygen evolution reaction[J]. Applied Surface Science, 2017, 416: 371-378.
[44]	TIEN Chien-Ping, LIANG Wuu-Jyh, KUO Pinglin, et al. Electric double layer capacitors with gelled polymer electrolytes based on poly(ethylene oxide) cured with poly(propylene oxide) diamines[J]. Electrochimica Acta, 2008, 53(13): 4505-4511.
[45]	ASHOK Venkatachalam, MATHI Selvam, SANGAMITHIRAI Muthukumaran, et al. Regulated bimetal-doped polyaniline: Amorphous-crumple-structured viable electrocatalyst for an efficient oxygen evolution reaction[J]. Energy & Fuels, 2022, 36(23): 14349-14360.
[46]	QIANG Chenchen, LIU Min, ZHANG Liang, et al. In situ growth of Ni-based metal-organic framework nanosheets on carbon nanotube films for efficient oxygen evolution reaction[J]. Inorganic Chemistry, 2021, 60(5): 3439-3446.
[47]	SUN Xuan, ZHANG Xiuxiu, LI Yuanli, et al. In situ construction of flexible V-Ni redox centers over Ni-based MOF nanosheet arrays for electrochemical water oxidation[J]. Small Methods, 2021, 5(10): e2100573.
[48]	TANG Lei, XIA Meihan, CAO Shiyu, et al. Operando identification of active sites in Co-Cr oxyhydroxide oxygen evolution electrocatalysts[J]. Nano Energy, 2022, 101: 107562.
[49]	LIN Yangming, YU Linhui, TANG Ling, et al. In situ identification and time-resolved observation of the interfacial state and reactive intermediates on a cobalt oxide nanocatalyst for the oxygen evolution reaction[J]. ACS Catalysis, 2022, 12(9): 5345-5355.
[50]	ZHOU Feng, CHEN Jiadong, YANG Yun, et al. Exceptionally active and stable RuO₂ by constructing p-n heterojunction between Co₃O₄ and RuO₂ for acidic water oxidation[J]. Applied Surface Science, 2023, 641: 158508.

FeNi₃-Fe₃O₄/CN催化剂的制备及其电催化析氧性能

Preparation of FeNi₃-Fe₃O₄/CN electrocatalysts and their electrocatalytic oxygen evolution performance

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 50

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张巍, 梁垚城, 伍乔, 付业昊, 尹艳山, 成珊, 阮敏, 刘涛, 周昭仪, 张凯凯, 李丹聪. 基于金属离子改性的Cu-SSZ-13催化剂在NH₃-SCR脱硝中的应用[J]. 化工进展, 2025, 44(7): 3879-3891.
[2]	卢朋, 张迪, 刘瑶瑶, 于万金, 刘武灿, 张建君. 气相脱氟化氢合成C₂氢氟烯烃催化剂的研究进展[J]. 化工进展, 2025, 44(7): 3907-3916.
[3]	高姣姣, 颜诗宇, 杨太顺, 谢尚志, 杨艳娟, 徐晶. 不同晶型Al₂O₃负载Ru催化剂对聚乙烯氢解的影响[J]. 化工进展, 2025, 44(7): 3917-3927.
[4]	孔灿, 刘雨函, 盛誉, 刘芳, 常化振. 聚苯胺增强氧化亚铜催化二氧化碳还原[J]. 化工进展, 2025, 44(6): 3144-3153.
[5]	姚如伟, 宋乐音, 牛琴琴, 李聪明. Na-S双助剂修饰铁基催化剂催化CO₂加氢制C₂₊醇[J]. 化工进展, 2025, 44(6): 3154-3162.
[6]	陈少伟, 陈奕, 牛江奇, 刘天奇, 黄建国, 陈焕浩, 范晓雷. 介质阻挡放电等离子体催化反应器研究进展及应用展望[J]. 化工进展, 2025, 44(6): 3175-3189.
[7]	王家慧, 李培雅, 杨福胜, 王斌, 方涛. 有机液态储氢载体甲基环己烷脱氢研究进展[J]. 化工进展, 2025, 44(6): 3208-3223.
[8]	张莹, 郑雪梅, 马爱元, 田时泓. 聚乙烯常规及微波催化热解产物分布特征的研究进展[J]. 化工进展, 2025, 44(6): 3224-3237.
[9]	石秀顶, 王永全, 曾静, 苏畅, 洪俊明. 纳米管状Co-N-C活化过碳酸盐降解四环素[J]. 化工进展, 2025, 44(6): 3041-3052.
[10]	李佩燚, 孙波龙, 刘瑞岩, 周歆尧, 刘瑞林, 胡园园, 徐功涛, 李新平. 海藻酸钠/二氧化钛复合多孔材料的制备及油水分离应用[J]. 化工进展, 2025, 44(6): 3053-3061.
[11]	谢武强, 张岭, 贺杠, 蒋里锋, 郑晰瑞, 张和鹏. CoTBrPP-PTAB-Cu电催化还原CO₂制甲烷[J]. 化工进展, 2025, 44(6): 3093-3100.
[12]	李红伟, 许涵侨, 赵燕, 刘耀宗, 滕志君, 季东, 李贵贤. 铂基催化剂电催化甲醇氧化研究进展与展望[J]. 化工进展, 2025, 44(6): 3443-3456.
[13]	孔肖阳, 刘振涛, 邹予桐, 王丹丹, 段爱军, 徐春明, 王喜龙. 多环芳烃加氢裂化制BTX催化剂研究进展[J]. 化工进展, 2025, 44(6): 3468-3485.
[14]	刘诗哲. 甲基环己烷脱氢催化体系的研究进展[J]. 化工进展, 2025, 44(6): 3486-3496.
[15]	武亚丽, 张效林, 高丽敏, 黄茂财, 蔡斌, 张继兵. 秸秆粉/纤维资源化利用技术进展[J]. 化工进展, 2025, 44(6): 3509-3523.