镍氧化膜对 H_2PO_2~- 电氧化的去活化效应

电化学（中英文） ›› 1999, Vol. 5 ›› Issue (3): 261-266.

镍氧化膜对 H_2PO_2~- 电氧化的去活化效应

蒋太祥,吴辉煌

厦门大学化学系!固体表面物理化学国家重点实验室厦门361005,厦门大学化学系!固体表面物理化学国家重点实验室厦门361005

收稿日期:1999-08-28 修回日期:1999-08-28 出版日期:1999-08-28 发布日期:1999-08-28

Deactivation of Nickel Oxide/Hydroxide to Electrooxidation of H 2PO - 2 Anions on Nickel Electrodes in Alkaline Solutions

Jiang Taixiang * Wu Huihuang

(Dept. of Chem.,Xiamen Univ. and State Key Lab. for Phys.Chem. of the Solid Surfaces, Xiamen 361005,P.R.China

Received:1999-08-28 Revised:1999-08-28 Published:1999-08-28 Online:1999-08-28

摘要/Abstract

摘要： 应用开路电位测量和循环伏安法研究碱性介质中Ｈ２ＰＯ－２在镍电极上的电氧化过程，并对镍氧化膜的去活化机理进行了探讨．结果表明，镍电极在碱性介质中由于氧化膜的快速形成而显示出明显的非催化活性．Ｈ２ＰＯ－２的氧化发生在较负的电位范围，ＨＰＯ２－３为氧化的最终产物．Ｈ２ＰＯ－２的氧化过程分为Ｈ２ＰＯ－２吸附、Ｐ－Ｈ键断裂、活性中间物形成及其氧化等步骤．Ｈ２ＰＯ－２与活性镍充分的相互作用是形成活性基团及随后氧化的必要条件．

关键词: 次亚磷酸盐, 电氧化, 镍电极

Abstract: Electrooxidation of hypophosphite anions on polycrystalline nickel in alkaline solutions has been investigated by cyclic voltammetry and open circuit potential measurements.The results are explained based on the mechanism that the first step of hypophosphite oxidation is the adsorption of hypophosphite ions on nickel,followed by the homolysis of its hydrogen bond with the formation of radicals.The oxidation of hypophosphite on nickel in alkaline medium occurs at lower potentials between ca.-0.8 V—-1.1 V(SCE)and phosphite ion is the only oxidation product.There is no indication of hypophosphite oxidation at higher potentials.Severe deactivation of the surface occurs when the nickel surface is covered with surface oxide/hydroxide films which separates the hypophosphite ion from nickel substrate.The results show that the rate of the anodic oxidation of hypophosphite depends strongly on the nature of the nickel substrate,operation temperature,hypophosphite concentration and sweep rate.

Key words: Hypophosphite, Electrooxidation, Nickel electrode

中图分类号:

O646

蒋太祥,吴辉煌. 镍氧化膜对 H_2PO_2~- 电氧化的去活化效应[J]. 电化学（中英文）, 1999, 5(3): 261-266.

Jiang Taixiang * Wu Huihuang . Deactivation of Nickel Oxide/Hydroxide to Electrooxidation of H 2PO - 2 Anions on Nickel Electrodes in Alkaline Solutions[J]. Journal of Electrochemistry, 1999, 5(3): 261-266.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/

https://electrochem.xmu.edu.cn/CN/Y1999/V5/I3/261

参考文献

1 　 Izu mi Ohno , Osa m u Wakabayashi , Shiro Haruya m a . Anodic oxidation of reductants in electroless plating . J. Electroche m . Soc .,1985 , 132 :2 3 23 2 　 Jusys Z, Liau konis J, Vaskelis A. The m echanis m of electroless Ni_ P deposition studied by electroche mical m assspectro m etry . J. Electroanal . Che m .,1992 ,325 :24 7 3 　 Dugasz J, Szasz A. Factors affecting the adhesion of electroless coatings . Surf . Coatings Tech nol .,1993 , 5 8 :57 4 　 Abrantes L M , Correia J P. On the m echanis m of electroless Ni_ P plating . J. Electroche m . Soc .,1994 ,141 :2356 5 　 Lukes R M . The m echanis m for the autocatalytic reduction of nickel by hypophosphite ion . Plating ,1964 , No .10 :969 6 　 Bin dra P, Tweedie J. Mechanism s of electroless m etal platin g :1 . Application of the m ixed potential theory . J. Electroche m . Soc .,19 83 ,130 :1 112 7 　 Gafin A H, Orchard S W . Current_potential relations for the half reactions in tw o electroless nickel platin g bathsusin g the quartz crystal microbalance electrode , J. Appl . Electroche m ,1992 ,22 :8 30 8 　 Podesta J J, Piatti R C V, Arvia A J. Volta m m etric behaviour of platinu m in aqueous solutions containing sodiu m hypophosphite . J. Appl . Electroche m ,1 990 ,20 :245 9 　 Burke L D , Lee B H. Oxidation of so m e reducing agents used in electroless plating baths at gold anodes in aqueous m edia . J. Appl . Electroche m ,1992 ,22 :48 10 　 Hahn F, Beden B, Croissant M J, La m y C. In situ uv visible reflectance spectroscopic investigation of thenickel electrode_alkaline solution interface . Electrochim ica Acta , 1986 ,31(3) :335 11 　 Burke L D , Whelan D P. Gro w th of an electrochro mic film on nickel in base un der potential cycling conditions . J. Electroanal . Che m .,1980 ,109 :385 12 　 Smith S F. The m echanics of electroless nickel deposition . Met . Finish . ,1979 ,7 7 :60 13 　 Abrantes L M , Bewick A, Kalaji M , Oliveira M C. Electrooxidation of hyop hosphite on single_crystal nickelelectrodes :an in situ I R study , J. Che m . Soc . , Faraday Trans ,1996 , 92(23) :4 663 14 　 Abrantes L M , Oliveira M C, Vieil E. A probe bea m deflection study of the hypophosp hite oxidation on anickel electrode , Electrochimica Acta ,19 96 , 41 :1 515 15 　 Abrantes L M , Oliveira M C, Correia J P, Be wick A, Kalaji M . In situ study of the electrooxidation of hypophoshite on a polycrystalline nickel electrode , J. Che m , Soc ., Faraday Trans .,1 997 ,93(6) :1 119

[1]	冯辛, 刘博文, 郭可鑫, 范林丰, 王根香, 次素琴, 温珍海. 基于阳极甘油氧化电催化的碱/酸混合电解制氢研究[J]. 电化学（中英文）, 2023, 29(2): 2215005-.
[2]	吴炜星, 王莹. 乙烯在钯圆盘电极的电化学氧化研究[J]. 电化学（中英文）, 2023, 29(1): 2215004-.
[3]	甘团杰, 武建平, 刘石, 区文俊, 凌彬, 康雄武. 低结晶度AuPt-Ru/CNTs合金异质结作为高效多功能电催化剂[J]. 电化学（中英文）, 2022, 28(8): 2201241-.
[4]	韦聚才, 石霖, 吴旭. 膜电极电解器电解脱硫废水制备硫酸铵副产氢[J]. 电化学（中英文）, 2022, 28(5): 2112211-.
[5]	彭浩, 孙惠军, 周志有, 申琳璠, 黄龙, 曹烁晖, 孙世刚. 基于硅基硼掺金刚石电极的电化学-原位核磁共振波谱电解池的设计、制备与可行性研究[J]. 电化学（中英文）, 2021, 27(3): 332-338.
[6]	张伟艺, 马宪印, 邹受忠, 蔡文斌. 铂和钯上丙三醇电氧化研究进展：从反应机理到催化材料[J]. 电化学（中英文）, 2021, 27(3): 233-256.
[7]	黄海清, 缪烨, 张新胜. 间接电氧化2-丁酮制备α-羟基缩酮的研究[J]. 电化学（中英文）, 2020, 26(3): 389-396.
[8]	陈维伟, 张飞凡, 杜佳亮, 王毅, 赵春林, 朱凯, 曹殿学, 王贵领. 泡沫镍载 NiCO₂O₄电极的制备及其催化 H₂O₂电氧化的性能[J]. 电化学（中英文）, 2020, 26(1): 96-102.
[9]	孙雍荣，杜春雨，韩国康，王雅静，高云智，尹鸽平. 可见光诱导提升Pt/g-C₃N₄纳米片甲酸氧化性能的研究[J]. 电化学（中英文）, 2018, 24(3): 262-269.
[10]	廖艳梅，武倩倩，张安伦，朱英红，马淳安. C-H键选择性直接电氧化研究[J]. 电化学（中英文）, 2017, 23(3): 276-282.
[11]	马翔宇，涂序国，何瑞楠，陈亚，朱桂生，邵守言，陈松. IrSnO_x电极制备及其在电氧化制备2,5-二氯苯酚中的应用[J]. 电化学（中英文）, 2017, 23(3): 327-331.
[12]	陈姿颖，武倩倩，张健青，朱英红，马淳安. 负载型离子液体在C-H键电氧化活化中的应用研究[J]. 电化学（中英文）, 2017, 23(1): 1-6.
[13]	吉维肖，王凤，钱江锋，曹余良，艾新平，杨汉西. 3, 4-乙烯二氧噻吩单体用作锂离子电池安全性改善添加剂的研究[J]. 电化学（中英文）, 2016, 22(3): 271-277.
[14]	王龙龙, 曹晓璐, 王亚骏, 平金豪, 李巧霞. Pd-Sb/C复合纳米催化剂对甲酸电催化氧化的性能研究[J]. 电化学（中英文）, 2015, 21(4): 368-374.
[15]	陈琼，朱英红，朱颖，李艳芳，马淳安*. 咪唑型离子液体对4–甲氧基甲苯的电氧化性能研究[J]. 电化学（中英文）, 2014, 20(5): 465-469.