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有机电化学及电化学工业近期研究专辑(华东理工大学张新胜教授、北京化工大学曾程初教授主编)

1-丁基-3-甲基咪唑醋酸盐和水组成的混合电解液中三价铬电沉积铬的研究

  • 罗维 ,
  • 钮东方 ,
  • 杜荣斌 ,
  • 王钧伟 ,
  • 汪竹青 ,
  • 徐衡 ,
  • 张新胜
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  • 1.华东理工大学化学工程国家重点实验室,上海200237;2. 石油化工新材料协同创新中心,安徽安庆 246011

收稿日期: 2016-11-25

  修回日期: 2017-02-07

  网络出版日期: 2017-03-01

基金资助

安徽省石油化工新材料协同创新中心资助

Electrochemical Deposition of Cr from Cr3+ in the Mixed Electrolyte of [BMIM]OAc/H2O

  • LUO Wei ,
  • NIU Dong-fang ,
  • DU Rong-bin ,
  • WANG Jun-wei ,
  • WANG Zhu-qing ,
  • XU Heng ,
  • ZHANG Xin-sheng
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  • 1.State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China; 2. Collaborative Innovation Center for Petrochemical New Materials, Anqing 246011, Anhui, China

Received date: 2016-11-25

  Revised date: 2017-02-07

  Online published: 2017-03-01

摘要

本文在[BMIM]OAc-H2O电解液中研究了Cr3+的电沉积反应. 经循环伏安研究表明, Cr3+的还原属于受扩散控制的分步还原过程, 即Cr3+ + e → Cr2+和Cr2+ + 2e → Cr0. 在40℃下通过Rendle-Sevcik方程计算得到Cr3+的扩散系数为1.2×10-8 cm2/s. 采用计时电流法探讨了Cr的三维瞬时成核机理. 对沉积的铬镀层进行了XRD、SEM表征, 结果表明经600℃氩气保护下煅烧后的镀层由Cr和Cr2O3纳米球状颗粒聚集而成, 其平均粒径为0.48μm. 对40℃,-3.0V条件下所得镀层进行EDX检测,发现Cr与O的能级峰十分明显,其中Cr的质量分数为83.8%. 通过在[BMIM]OAc、[BMIM]BF4和[BMIM]PF6三种离子液体体系中电镀得到的Cr镀层质量的比较, 表明OAc-的确有利于Cr的电沉积.

本文引用格式

罗维 , 钮东方 , 杜荣斌 , 王钧伟 , 汪竹青 , 徐衡 , 张新胜 . 1-丁基-3-甲基咪唑醋酸盐和水组成的混合电解液中三价铬电沉积铬的研究[J]. 电化学, 2017 , 23(3) : 332 -339 . DOI: 10.13208/j.electrochem.161053

Abstract

The electrochemical reduction of trivalent chromium ion (Cr3+) to Cr in 1-butyl-3-methylimidazolium acetate ([BMIM]OAc)-H2O mixed electrolyte was investigated. The cyclic voltammograms showed that the electroreduction of Cr3+ in the mixed electrolyte occurred in a two-step process, namely, Cr3+ + e → Cr2+ and Cr2+ + 2e→ Cr0, controlled by the diffusion of Cr3+ to the electrode. The diffusion coefficient of Cr3+ was 1.2×10-8 cm2/s at 40 ℃ obtained by Rendle-Sevcik equation. The chronoamperomograms of the Cr3+ electrodeposition confirmed the three-dimensional instantaneous nucleation mechanism of Cr. The XRD and SEM characterizations on the Cr coating after calcining in argon atmosphere at 600℃ revealed that the coating was composed of Cr and chromium oxide (Cr2O3) nanoparticles with an average particle size of 0.48 μm. The elements of Cr and O were obviously detected from the coating obtained at 40℃ and -3.0V by EDX and the mass fraction of Cr reached 83.8%. Comparison in the qualities of coating layers prepared by Cr electrodepositions in [BMIM]OAc, [BMIM]BF4 and [BMIM]PF6 electrolytes indicated that the OAc- was presented in favor of Cr3+ reduction.
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