碳毡基体上电沉积Ni-Mo合金及其催化析氢性能

摘要

以碳毡为基体，采用瓦特型镀镍工艺电沉积镍，获得碳镍（C-Ni）电极，然后在离子液体体系中以C-Ni为基体电沉积Ni-Mo合金。采用扫描电镜和X射线衍射仪对合金电极的表面形貌和结构进行了表征，通过阴极极化曲线、交流阻抗等电化学测试研究了其析氢催化性能。实验结果表明，制得的Ni-Mo合金中Mo的质量百分含量约为5.12%，平均晶粒尺寸约为2.2 nm，为纳米晶结构；极化曲线测试表明，当电流密度为0.1 A·cm^-2时，Ni-Mo/C-Ni合金电极催化析氢电位较C-Ni电极正移108 mV，较碳毡正移557 mV，较水溶液中沉积的紫铜基Ni-Mo合金电极正移约50 mV；连续电解和断电流实验结果表明Ni-Mo/C-Ni合金电极具有良好的电化学稳定性，实用前景广阔。

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	王宏智
	张晓振
	黄波
	张卫国
	姜世圣
	姚素薇

关键词：碳毡；离子液体；电沉积； Ni-Mo合金；催化析氢

Abstract：

Based on carbon felt, C-Ni electrode was electrodeposited with Watt nickel plating process; then the Ni-Mo alloy electrode was obtained based on C-Ni electrode that has been prepared in ionic liquids system. Its surface morphology and structure were performed with scanning electric microscope and X-ray diffractometer, respectively; and its property of electrochemical catalyzed hydrogen evolution has been studied by means of cathodic polarization curves and A.C. impedance technique. Experimental results suggest that the prepared C-Ni/Ni-Mo alloy contains about 5.12% Mo and has a nanocrystalline structure with average crystallites sizes of 2.2 nm; and polarization curves indicate that the catalytic hydrogen evolution potential of Ni-Mo/C-Ni alloy electrode deposited in ionic liquid has a positively shift of about 108 mV compared with C-Ni electrode and about 557 mV compared with C felt electrode and about 50 mV compared with Ni-Mo based on Cu substrate in aqueous solution under the current density of 0.1 A·cm²; the potential fluctuation of Ni-Mo/C-Ni alloy electrode is slight during a prolonged electrolysis, and the potential is able to recover rapidly after short current interruption. So Ni-Mo/C-Ni alloy electrode shows a good electrochemical stability.

Keywords： carbon felt； ionic liquids； electrodeposition； Ni-Mo alloy； catalytic hydrogen evolution

Received 2015-02-03;

Corresponding Authors: 张卫国,E-mail:zwg@tju.edu.cn。 Email: zwg@tju.edu.cn

About author: 王宏智(1973-),男,副教授,研究方向为金属基复合材料。

引用本文:

王宏智, 张晓振, 黄波, 张卫国, 姜世圣, 姚素薇.碳毡基体上电沉积Ni-Mo合金及其催化析氢性能[J]. 化学工业与工程, 2017,34(1): 53-59

Wang Hongzhi, Zhang Xiaozhen, Huang Bo, Zhang Weiguo, Jiang Shisheng, Yao Suwei.Electrodeposition of Ni-Mo Alloy from Ionic Liquids and Its Catalytic Properties for Hydrogen Evolution[J]. Chemcial Industry and Engineering, 2017,34(1): 53-59

[1] 高鹏, 曹立新, 屠振密. 镍合金析氢电极研究概述[J]. 材料保护, 2010, 43(4):68-71 Gao Peng, Cao Lixin, Tu Zhenmi. Summary of nickel alloy electrodes for hydrogen evolution[J]. Materials Protection, 2010, 43(4):68-71(in Chinese)
[2] 高峻峰, 孟令局, 玄兆坤, 等. 去合金化法制备多孔镍-硫-钴电极及其催化析氢性能[J]. 电镀与涂饰, 2013, 32(11):5-8 Gao Junfeng, Meng Lingju, Xuan Zhaokun, et al. Electrocatalytic behavior of hydrogen evolution on porous nickel-sulfur-cobalt electrode prepared by dealloying method[J]. Electroplating and Finishing, 2013, 32(11):5-8(in Chinese)
[3] Trasatti S. Electrocatalysis of hydrogen evolution:Progress in cathode activation[J]. Advances in Electrochemical Science and Engineering, 1992, 2:1-85
[4] Jordanov S H, Paunovic' P, Popovski O, et al. Electrocatalysts in the last 30 years-From precious metals to cheaper but sophisticated complex systems[J]. Bull Chem Technol Macedonia, 2004, 23(2):101-112
[5] Dominguez-Crespo M A, Torres-Huerta A M, Brachetti-Sibaja B, et al. Electrochemical performance of Ni-RE (RE=rare earth) as electrode material for hydrogen evolution reaction in alkaline medium[J]. International Journal of Hydrogen Energy, 2011, 36(1):135-151
[6] Rosalbino F, Maccio D, Saccone A, et al. Fe-Mo-R (R=rare earth metal) crystalline alloys as a cathode material for hydrogen evolution reaction in alkaline solution[J]. International Journal of Hydrogen Energy, 2011, 36(3):1965-1973
[7] 刘萍, 唐致远, 宋全生, 等. Ni-Mo合金电极的制备条件对其析氢性能的影响[J]. 电镀与精饰, 2006, 28(3):11-14 Liu Ping, Tang Zhiyuan, Song Quansheng, et al. Effect of preparation condition of Ni-Mo alloy on electrocatalytic activity for hydrogen evolution[J]. Plating and Finishing, 2006, 28(3):11-14(in Chinese)
[8] 魏海兴, 周振芳, 吕东方, 等. 脉冲电沉积制备Ni-Mo合金析氢电极[J]. 舰船科学技术, 2011, 33(9):124-127 Wei Haixing, Zhou Zhenfang, Lü Dongfang, et al. Pulse plating of Ni-Mo alloy electrodes for hydrogen evotion[J]. Ship Science and Technology, 2011, 33(9):124-127(in Chinese)
[9] 张卫国, 王飙, 刘春松, 等. 离子膜电解槽用纳米Ni-Mo合金阴极的制备及其催化析氢性能[J]. 氯碱工业, 2006, 12:12-14 Zhang Weiguo, Wang Biao, Liu Chunsong, et al. The preparation of nano-Ni-Mo alloy cathodes for ion-exchange membrance electrolyzers and their catalytic hydrogen evolution property[J]. Chlor-Alkali Industry, 2006, 12:12-14(in Chinese)
[10] 张锁江,徐春明,吕兴梅,等. 离子液体和绿色化学[M]. 北京:科学出版社, 2009 Zhang Suojiang, Xu Chunming, Lü Xingmei, et al. Ionic Liquids and Green Chemistry[M]. Beijing:Science Press, 2009
[11] You Y, Gu C, Wang X, et al. Electrodeposition of Ni-Co alloys from a deep eutectic solvent[J]. Surface and Coatings Technology, 2012, 206(17):3632-3638
[12] Endres F, MacFarlane D, Abbott A. Electrodeposition from Ionic Liquids[M]. New York:John Wiley & Sons, 2008
[13] 尹小梅, 徐联宾, 单南南, 等. TMPAC-AlCl₃离子液体中恒电流电沉积铝[J]. 化工学报, 2012, 64(3):1022-1029 Yin Xiaomei, Xu Lianbin, Shan Nannan, et al. Constant current eletrodeposition of alumnium from TMPAC-AlCl₃ ionic liquids[J]. CIESC Journal, 2012, 64(3):1022-1029(in Chinese)
[14] 杨志, 闫瑞景, 梁镇海. 离子液体中脉冲电镀[J]. 材料保护, 2013, 46(1):31-34 Yang Zhi, Yan Ruijing, Liang Zhenhai. Pulse aluminum electroplating on Cu substrate in ionic liquid medium[J]. Materials Protection, 2013, 46(1):31-34(in Chinese)
[15] Zheng Y, Zhang S, Lv X, et al. Low-Temperature electrodeposition of aluminium from Lewis acidic 1-allyl-3-methylimidazolium chloroaluminate ionic liquids[J]. Chin J Chem Eng, 2012, 20(1):130-139
[16] Zhang Q, Vigier K D O, Royer S, et al. Deep eutectic solvents:Syntheses, properties and applications[J]. Chemical Society Reviews, 2012, 41(21):7108-7146
[17] Abbott A P, Capper G, Davies D L, et al. Novel solvent properties of choline chloride/urea mixtures[J]. Chemical Communications, 2003, (1):70-71
[18] 王小娟, 李慧, 王娇, 等. 钴锌合金在氯化胆碱-尿素离子液体中的电沉积行为[J]. 材料保护, 2010, 43(3):1-5 Wang Xiaojuan, Li Hui, Wang Jiao, et al. Eletrodeposition of Co-Zn alloy in choline chloride-urea ionic liquid[J]. Materials Protection, 2010, 43(3):1-5(in Chinese)
[19] Florea A, Anicai L, Costovici S, et al. Ni and Ni alloy coatings electrodeposited from choline chloride-based ionic liquids-electrochemical synthesis and characterization[J]. Surface and Interface Analysis, 2010, 42(6/7):1271-1275
[20] Abbott A P, Capper G, McKenzie K J, et al. Electrodeposition of zinc-tin alloys from deep eutectic solvents based on choline chloride[J]. Journal of Electroanalytical Chemistry, 2007, 599(2):288-294
[21] Abbott A P, El-Ttaib K, Frisch G, et al. Electrodeposition of copper composites from deep eutectic solvents based on choline chloride[J]. Physical Chemistry Chemical Physics, 2009, 11(21):4269-4277
[22] Abbott A P, El-Ttaib K, Frisch G, et al. The electrodeposition of silver composites using deep eutectic solvents[J]. Physical Chemistry Chemical Physics, 2012, 14(7):2443-2449
[23] 王宏智, 黄波, 张卫国, 等. 深共融溶剂中电沉积Ni-Mo合金及其催化析氢性能[J]. 化工学报, 2014, 65(11):4524-4529 Wang Hongzhi, Huang Bo, Zhang Weiguo, et al. Electrodeposition of Ni-Mo alloy from deep eutectic solvents and its catalytic properities for hydrogen generation[J]. CIESC Journal, 2014, 65(11):4524-4529(in Chinese)
[24] Lu G, Zangari G. Corrosion resistance of ternary Ni-P based alloys in sulfuric acid solutions[J]. Electrochimica Acta, 2002, 47(18):2969-2979
[25] Warren B E. X-Ray diffraction[M]. Middlesex:Courier Corporation, 1969
[26] Jeyaprabha C, Sathiyanarayanan S, Venkatachari G. Effect of cerium ions on corrosion inhibition of PANI for iron in 0.5 M H₂SO₄[J]. Applied Surface Science, 2006, 253(2):432-438
[27] Liu X, Chen S, Ma H, et al. Protection of iron corrosion by stearic acid and stearic imidazoline self-assembled monolayers[J]. Applied Surface Science, 2006, 253(2):814-820
[28] Brewer L. The generalized Lewis acid-base theory:Surprising recent developments[J]. J Chem Educ, 1984, 61:101-104
[29] Brewer L. Bonding and structures of transition metals[J]. Science, 1968, 161(3837):115-122
[30] Parsons R. The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen[J]. Transactions of the Faraday Society, 1958, 54:1053-1063
[31] 李贺, 姚素薇, 张卫国, 等. 电化学技术制备析氢电极材料的研究进展[J]. 化工进展, 2005, 24(7):718-722 Li He, Yao Suwei, Zhang Weiguo, et al. Recent progress in electrochemical preparation of electrode materials for hydrogen evolution[J]. Chemical Industry and Engineering Progress, 2005, 24(7):718-722(in Chinese)
[32] Liu H, He P, Li Z, et al. High surface area nanoporous platinum:Facile fabrication and electrocatalytic activity[J]. Nanotechnology, 2006, 17(9):2167-2173
[33] Liu H, Liu Y, Li J. Ionic liquids in surface electrochemistry[J]. Physical Chemistry Chemical Physics, 2010, 12(8):1685-1697