Preparation of NiCoFe electrodes for electrochemical deoxidation by one-step electrodeposition

doi:10.19965/j.cnki.iwt.2023-0551

Abstract

Abstract:

Aiming at the high cost and poor effect of catalytic materials for cathodic oxygen reduction reaction(ORR) in electrochemical deoxygenation, NiCoFe ternary alloy was efficiently prepared by electrodeposition under different current densities, and the morphology and structure of the alloy material were characterized and analyzed, which showed that NiCoFe alloy had a fluffy cauliflower-like surface morphology and alloy crystalline structure. The ORR performance of the NiCoFe alloy was tested in a three-electrode system at different current densities. When the electrodeposition current density was 1.0 A/cm², the alloy was obtained with a half-wave potential of 0.782 V, an onset potential of 0.936 V, and a limiting current density of 2.9 mA/cm². The rotating ring disk electrode(RRDE) test showed that the number of transferred electrons of the alloywas 3.52, which was close to that of the four-electron transfer of commercial Pt/C catalysts. An electrochemical deoxidation test equipment was designed to investigate the removal effect of NiCoFe alloy as a cathode electrode on dissolved oxygen in simulated industrial water. The results showed that the deoxidation rate of NiCoFe cathode was over 99%, making it an excellent ORR electrocatalyst material.

Key words: electrochemistry, deoxidation, electrocatalyst, oxygen reduction reaction, NiCoFe

摘要：

针对电化学脱氧中阴极氧还原反应（ORR）所用催化材料成本高、效果差的问题，在不同电流密度下通过电沉积法高效制备NiCoFe三元合金，并对合金材料的形貌和结构进行表征和分析，结果表明所制备NiCoFe合金有着蓬松的花椰菜状表面形貌和合金晶型结构。在三电极体系中对不同电流密度下制备的NiCoFe合金进行ORR性能测试，结果表明，当电沉积电流密度为1.0 A/cm²时，NiCoFe合金的半波电位为0.782 V，起始电位为0.936 V，极限电流密度为2.9 mA/cm²，盘环电极（RRDE）测试显示合金的转移电子数为3.52，接近于商用Pt/C催化剂的四电子转移。设计电化学脱氧小试设备用于考察NiCoFe合金作为阴极电极时对于模拟工业水中溶解氧的去除效果，结果表明NiCoFe阴极的脱氧率达99%以上，是一种性能优异的ORR电催化材料。

关键词: 电化学, 脱氧, 电催化剂, 氧还原反应, NiCoFe

CLC Number:

X703.1

Ximin WANG, Deze YU, Chenxin XIE, Tianzhen ZHU, Guanglei QIAN, Guangyuan YAO. Preparation of NiCoFe electrodes for electrochemical deoxidation by one-step electrodeposition[J]. Industrial Water Treatment, 2024, 44(6): 127-134.

王锡民, 于德泽, 谢陈鑫, 朱田震, 钱光磊, 姚光源. 一步电沉积法制备NiCoFe电极用于电化学脱氧的研究[J]. 工业水处理, 2024, 44(6): 127-134.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-0551

https://www.iwt.cn/EN/Y2024/V44/I6/127

Figures/Tables 13

Fig.1 Schematic diagram of electrochemical deoxidation device

Fig.2 SEM of NiCoFe alloys electrodeposition at different current densities

Fig.3 XRD patterns of electrodeposited NiCoFe alloys at different current densities

Table 1 The elemental composition of electrodeposited NiCoFe alloys at different current densities

电流密度/（A·cm^-2）	原子数分数/%
电流密度/（A·cm^-2）	Fe	Co	Ni
0.3	6.4	31.1	62.5
0.5	9.3	31.6	59.1
1.0	22.1	32.7	45.2
1.5	10.8	32.0	57.2

Fig.4 Distribution of Fe，Co and Ni elements in NiCoFe alloy

Fig.5 CV diagrams of different metallic materials（a） and NiCoFe alloys（b） prepared under different current densities

Fig.6 LSV curves of NiCoFe alloys prepared under different current densities

Fig.7 EIS patterns of different metallic materials（a） and NiCoFe alloys（b） prepared under different current densities

Fig.8 Stability test curves of electrodeposited NiCoFe alloys at different current densities

Fig.9 Disk ring current density of NiCoFe alloy obtained by RRDE test

Table 2 Oxygen removal properties of different metal materials

材料	电流/A	电压/V	阴极进水流量/（L·h^-1）	阳极进水流量/（L·h^-1）	出水溶解氧/（μg·L^-1）
铜片	0.3	5.10	9.0	3.6	2 300
不锈钢片	0.3	5.00	9.0	3.6	3 600
钛片	0.3	5.30	9.0	3.6	5 400
NiCoFe	0.3	5.10	9.0	3.6	400

Fig.10 Deoxidation performance of electrodeposited NiCoFe alloys at different current densities for different time periods

Table 3 Oxygen removal properties of NiCoFe alloys at different current

电流/A	电压/V	阴极进水流量/（L·h^-1）	阳极进水流量/（L·h^-1）	出水溶解氧/（μg·L^-1）
0.053（理论）	2.15	1.5	0.6	90
0.106（2倍）	3.10	1.5	0.6	35
0.161（3倍）	3.95	1.5	0.6	38
0.212（4倍）	4.30	1.5	0.6	40

References 24

1	肖公奎，刘元法，贺高红，等. 中空纤维膜接触器脱除水中溶解氧的研究［J］. 渤海大学学报（自然科学版），2008，29（4）：308-313. doi:10.3969/j.issn.1673-0569.2008.04.003
	XIAO Gongkui， LIU Yuanfa， HE Gaohong，et al. Removal of dissolved oxygen from water using hollow fiber membrane contactor［J］. Journal of Bohai University（Natural Science Edition），2008，29（4）：308-313. doi:10.3969/j.issn.1673-0569.2008.04.003
2	袁益超，王玥，陈昱，等. 热力除氧器性能试验研究［J］. 工业水处理，2017，37（1）：53-56. doi:10.11894/1005-829x.2017.37(1).013
	YUAN Yichao， WANG Yue， CHEN Yu，et al. Experimental research on the performance of thermal deaerators［J］. Industrial Water Treatment，2017，37（1）：53-56. doi:10.11894/1005-829x.2017.37(1).013
3	许建芬. 余热电站真空除氧系统的节能改造［J］. 应用能源技术，2017（3）：27-29. doi:10.3969/j.issn.1009-3230.2017.03.007
	XU Jianfen. Energy-saving transformation of vacuum deaeration system in waste heat power station［J］. Applied Energy Technology，2017（3）：27-29. doi:10.3969/j.issn.1009-3230.2017.03.007
4	路珈，王泽鑫，惠艳蓉. 石油石化行业锅炉净水除氧技术的运用［J］. 石化技术，2023，30（7）：67-69. doi:10.3969/j.issn.1006-0235.2023.07.023
	LU Jia， WANG Zexin， HUI Yanrong. Application of deoxygenation technology for boiler water purification in petroleum and petrochemical industry［J］. Petrochemical Industry Technology，2023，30（7）：67-69. doi:10.3969/j.issn.1006-0235.2023.07.023
5	DURDEVIC P， YANG Z. Potential use of real-time dissolved oxygen sensors for oxygen scavenging feedback control［J］. IOP Conference Series：Materials Science and Engineering，2019，504：012098. doi:10.1088/1757-899x/504/1/012098
6	曾庆峰，刘富余，赵金海. 石油石化行业锅炉进水除氧技术应用进展［J］. 石油石化节能，2017，7（3）：13-14. doi:10.3969/j.issn.2095-1493.2017.03.005
	ZENG Qingfeng， LIU Fuyu， ZHAO Jinhai. Application process of deoxygenation technology for boiler water supply in petroleum and petrochemical industry［J］. Energy Conservation in Petroleum & Petrochemical Industry，2017，7（3）：13-14. doi:10.3969/j.issn.2095-1493.2017.03.005
7	毛丽燕，张文华. 海绵铁催化除氧及脱铁装置的使用不当对锅炉缓蚀的影响［J］. 当代化工，2016，45（5）：986-987. doi:10.3969/j.issn.1671-0460.2016.05.043
	MAO Liyan， ZHANG Wenhua. Influence of incorrect use of sponge iron catalytic deoxidization and iron removal device on the boiler corrosion inhibition［J］. Contemporary Chemical Industry，2016，45（5）：986-987. doi:10.3969/j.issn.1671-0460.2016.05.043
8	ZEKOS I， STACK M M. A note on a design protocol for deoxygenation of water［J］. Electrochemistry Communications，2019，103：12-16. doi:10.1016/j.elecom.2019.04.009
9	VUORILEHTO K， TAMMINEN A， YLASAARI S. Electrochemical removal of dissolved oxygen from water［J］. Journal of Applied Electrochemistry，1995，25（10）：973-977. doi:10.1007/bf00241593
10	HOLUBOWITCH N， OMOSEBI A， GAO Xin，et al. Membrane-free electrochemical deoxygenation of aqueous solutions using symmetric activated carbon electrodes in flow-through cells［J］. Electrochimica Acta，2018，297（5）：163-172. doi:10.1016/j.electacta.2018.11.106
11	MAREI M M， ROUSSEL T J， KEYNTON R S，et al. Electrochemical dissolved oxygen removal from microfluidic streams for LOC sample pretreatment［J］. Analytical Chemistry，2014，86（17）：8541-8546. doi:10.1021/ac501398f
12	张显. 非贵金属电催化剂的合成及其性能研究［D］. 合肥：中国科学技术大学，2018.
	ZHANG Xian. Synthesis and applications of non-precious metal electrocatalysts［D］. Hefei：University of Science and Technology of China，2018.
13	GUZMÁN-VARGAS A， VAZQUEZ-SAMPERIO J， OLIVER-TOLENTINO M A，et al. Influence of cobalt on electrocatalytic water splitting in NiCoFe layered double hydroxides［J］. Journal of Materials Science，2018，53（6）：4515-4526. doi:10.1007/s10853-017-1882-z
14	SIAL M A Z G， LIN Haifeng， WANG Xun. Microporous 2D NiCoFe phosphate nanosheets supported on Ni foam for efficient overall water splitting in alkaline media［J］. Nanoscale，2018，10（27）：12975-12980. doi:10.1039/c8nr03350a
15	RAFAILOVIĆ L D， GAMMER C， KLEBER C，et al. Synthesis and characterization of electrodeposited hierarchical nanodendritic NiCoFe alloy powders［J］. Journal of Alloys and Compounds，2012，543：167-171. doi:10.1016/j.jallcom.2012.07.081
16	BUDI S， MANAF A. The effects of saccharin on the electrodeposition of NiCoFe films on a flexible substrate［J］. Materials Research Express，2021，8（8）：086513. doi:10.1088/2053-1591/ac1a2c
17	SIAL M A Z G， LIU Shiyu， ZOU Jizhao，et al. NiCoFe alloy multishell hollow spheres with lattice distortion to trigger efficient hydrogen evolution in acidic medium［J］. Sustainable Energy & Fuels，2019，3（12）：3310-3317. doi:10.1039/c9se00504h
18	JEUNG W， KIM H K， LEE J O. The effect of composition and current condition on magnetic properties of Co-Fe-Ni soft magnetic alloy［J］. Journal of the Korean Magnetics Society，2005，15（4）：241-245. doi:10.4283/jkms.2005.15.4.241
19	BUDI S， MUHAB S， PURWANTO A，et al. Effect of the electrodeposition potential on the magnetic properties of FeCoNi films［J］. Materials Science-Poland，2019，37（3）：389-394. doi:10.2478/msp-2019-0044
20	BUDI S， KURNIAWAN B， MOTT D M，et al. Comparative trial of saccharin-added electrolyte for improving the structure of an electrodeposited magnetic FeCoNi thin film［J］. Thin Solid Films，2017，642：51-57. doi:10.1016/j.tsf.2017.09.017
21	GUO Manying， YE Lin， ZHAO Lijun. Solid-state-grinding method to synthesize NiCoFe alloy/NiCoFe-OH nanosheets for asymmetric supercapacitor［J］. Journal of Alloys and Compounds，2021，850：156787. doi:10.1016/j.jallcom.2020.156787
22	郭文君，李丹丹，王强，等. NiCoFe LDH阳极析氧催化剂的制备及性能研究［J］. 太阳能学报，2021，42（5）：46-53. doi:10.19912/j.0254-0096.tynxb.2019-0116
	GUO Wenjun， LI Dandan， WANG Qiang，et al. Preparation and properties of ni co fe ldh anodic oxygen evolution catalyst［J］. Acta Energiae Solaris Sinica，2021，42（5）：46-53. doi:10.19912/j.0254-0096.tynxb.2019-0116
23	葛升，闵洛夫，费洪达，等. 一步电沉积制备高活性高稳定镍铁合金析氧电催化剂［J］. 化学工业与工程，2022，39（2）：41-49.
	GE Sheng， MIN Luofu， FEI Hongda，et al. Highly efficient and durable Ni-Fe alloy catalyst towards OER via one-step electrodeposition［J］. Chemical Industry and Engineering，2022，39（2）：41-49.
24	赵宗涛. 纳米复合电催化剂的制备及其在氧还原中的应用研究［D］. 上海：东华大学，2022.
	ZHAO Zongtao. Preparation of nanocomposite electrocatalysts for application in oxygen reduction reaction［D］. Shanghai：Donghua University，2022.

[1]	Jing JIANG, Zhaolun CUI, Chuyan ZHANG, Nan HUANG. Electrochemical oxidation of p-nitrophenol on boron-doped diamond film electrode [J]. Industrial Water Treatment, 2025, 45(3): 157-164.
[2]	Huiyuan LIU, Xinhua LIU, Junxia GUAN, Ying WANG, Shili SHU, Lei WANG, Yulong LI, Zixuan YAN, Yubo XIA, Jiarui DU, Xin ZHOU, Heqiong XIANG, Xinyuan ZHANG. Corrosion inhibition properties of polyepoxysuccinic acid derivatives in acid media [J]. Industrial Water Treatment, 2025, 45(3): 137-143.
[3]	Hongwei ZHANG, Xiaojing XI, Wenjie TIAN, Huiying ZHANG, Xiaomeng MA, Minjie WEI, Huajun CHEN. Flexible carbon-fiber/g-C₃N₄ nanosheet arrays as recyclable photocatalysts and photoelectrocatalysts [J]. Industrial Water Treatment, 2024, 44(8): 99-106.
[4]	Fan XIA, Weihao ZHONG, Wei MAO, Hongtao YU. Construction of an electrochemical reactor for efficient water softening via promoting CaCO₃ nucleation in liquid phase [J]. Industrial Water Treatment, 2024, 44(7): 83-88.
[5]	Wei MAO, Hongtao YU. Emerging problems and strategies of electrochemical water softening technology [J]. Industrial Water Treatment, 2023, 43(7): 32-40.
[6]	Yicheng LI, Xiaohong GUAN, Lanju KONG. Performance of corrosion inhibitor of high salt oxygen system in Xinjiang Oilfield [J]. Industrial Water Treatment, 2023, 43(6): 143-149.
[7]	Ruting LIANG, Haifeng ZHUANG. Advances in the enhancement of anaerobic degradation of organic matter by magnetic carbon coupled with microcurrent [J]. Industrial Water Treatment, 2023, 43(5): 1-8.
[8]	Daobin MU, Jun YANG, Chenglei ZHANG, Rongjian NIE. Research on the application of water saving technology of circulating water controlled by electrochemistry and agent combining treatment [J]. Industrial Water Treatment, 2023, 43(5): 188-193.
[9]	Lixin JIANG, Nan WU, Pengtang WANG, Shengfeng MA. Application of ozone and electrochemical oxidation in recycling and treatment of fine chemical wastewater [J]. Industrial Water Treatment, 2023, 43(11): 61-65.
[10]	Jiajin CHEN,Han XU,Zhihao ZHANG,Xiaoli YANG. Research progress on the mechanism and influence of nitrogen removal by bioelectrochemical systems in wastewater [J]. Industrial Water Treatment, 2022, 42(3): 23-32.
[11]	Zekun YANG, Yong LIU, Haitao YANG, Chaoquan HU, Hongtao LI, Hailong JING. Preparation of titanium suboxide electrode and its application in wastewater treatment [J]. Industrial Water Treatment, 2022, 42(11): 56-64.
[12]	Songtao LIU, Hailong XU, Xiaomei DANG, Lipeng WANG, Qingzhuo SI, Chuanmin CHEN. Membrane electrolysis used in circulating cooling water treatment [J]. Industrial Water Treatment, 2022, 42(10): 154-159.
[13]	Huafang NIE, Qingfeng YANG, Dengke LIU, Yangqiao LIU. Co₃O₄-titanium-based nanoelectrode for nitrate removal from industrial wastewater [J]. Industrial Water Treatment, 2022, 42(10): 84-90.
[14]	Yongsheng Chen,Dexiang Liao,Fuqiang Wei,Chao Hu,Jiaqi Ju,Boyang Liu. Research progress in the treatment of pollutants by electro activated persulfate with different electrodes [J]. Industrial Water Treatment, 2021, 41(6): 141-148.
[15]	Shuilin Cheng,Min'ge Yang,Junbo Wang,Chuan Zhao,Songtao Liu,Yuan Shen. Study on electrochemical removal of phosphorus from wastewater [J]. Industrial Water Treatment, 2021, 41(4): 113-116.

Please choose a citation manager

Content to export