An in situ scanning tunneling microscopic study of electrodeposition of bismuth on Au(111) in a 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid Precursor adsorption and underpotential deposition

An in situ scanning tunneling microscopic study of electrodeposition of bismuth on Au(111) in a 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid Precursor adsorption and underpotential deposition
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1-丁基-3-甲基咪唑鎓四氟硼酸盐离子液体中铋在 Au(111) 上电沉积的原位扫描隧道显微研究前驱体吸附和欠电位沉积

DOI:
10.1016/j.electacta.2010.05.023
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发表时间:
2010-11
影响因子:
6.6
通讯作者:
Mao, Bing-Wei
Mao, Bing-Wei
中科院分区:
材料科学2区
文献类型:
--
作者:
Fu, Yong-Chun;Su, Yu-Zhuan;Zhang, Hai-Ming;Yan, Jia-Wei;Xie, Zhao-Xiong;Mao, Bing-Wei

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本文采用循环伏安法和原位扫描隧道显微镜(STM)研究了BiCl3在BMIBF4离子液体中欠电势区在Au(111)表面的电沉积。循环伏安图显示了几个分别与 Bi 的欠电位沉积 (UPD) 和 UPD 沉积物溶解相关的阴极和阳极峰,相对于 Pt 准参比电极,电位范围在 -0.38 和 -0.7V 之间。原位 STM 结果表明,在 Bi UPD 之前存在 BiCl3 前体吸附阶段。 BiCl3 的吸附导致形成具有 Au(111)(10×10) 结构的独特六方和三方超分子组装体。 Bi UPD的初始阶段是在-0.5V下形成由Bi三角形团簇组成的Au(111)(7×7) R21.8° Adlayer结构。在-0.6V时发生结构转变,产生由排列良好的Bi三角簇组成的独特的“拉链状”双链图案,可以用Au(111)(5×25√3/3)结构模型表示。无论欠电势偏移如何,由六个 Bi 原子组成的三角簇似乎是 Bi UPD Adlayer 的主要特征元素单元。这些特征与在含 Bi(III) 的酸性水溶液以及氯铝离子液体中观察到的特征显着不同,但与 BMIBF4 离子液体中 Sb UPD 的特征相似,这揭示了溶剂对半金属电沉积的深刻影响。
In this article, the electrodeposition of Bi on Au(111) surface in the underpotential region in BMIBF4ionic liquid containing BiCl3is studied by cyclic voltammetry and in situ scanning tunneling microscopy (STM). The cyclic voltammogram shows several cathodic and anodic peaks associated with underpotential deposition (UPD) of Bi and dissolution of the UPD deposit, respectively, in the potential region between −0.38 and −0.7V versus Pt quasi-reference electrode. In situ STM results indicate there is a BiCl3precursor adsorption stage prior to the Bi UPD. The adsorption of BiCl3leads to the formation of unique hexagonal and trigonal supramolecular assembly with a Au(111)(10×10) structure. The initial stage of Bi UPD proceeds with the formation of Au(111)(7×7) R21.8° adlayer structure composed of Bi trigonal clusters at −0.5V. A structural transformation occurred at −0.6V resulting in a unique “zipper-like” double-chain pattern composed of well-aligned Bi trigonal clusters which can be denoted by Au(111)(5×25√3/3) structural model. The trigonal clusters composed of six Bi atoms seem to be the main characteristic elemental units of Bi UPD adlayer regardless of underpotential shift. These features are dramatically different from those observed in Bi(III)-containing acidic aqueous solutions as well as in chloroaluminated ionic liquid, but are similar to those of Sb UPD in BMIBF4ionic liquid, which reveals profound solvent effects on the electrodeposition of semimetals.
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