Silicon (100) Electrodes Resistant to Oxidation in Aqueous Solutions: An Unexpected Benefit of Surface Acetylene Moieties
Silicon (100) Electrodes Resistant to Oxidation in Aqueous Solutions: An Unexpected Benefit of Surface Acetylene Moieties
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DOI：
10.1021/la803710d
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发表时间：
2009-02-17
期刊：
影响因子：
3.9
通讯作者：
Gooding, J. Justin
中科院分区：
文献类型：
--
作者：
Ciampi, Simone;Eggers, Paul K.;Gooding, J. Justin
本文报道了在高掺杂Si（100）上用点击反应将炔基封端的烷基单分子膜官能化为二茂铁衍生物。氢封端的硅表面与二炔物种的反应显示出提供非常稳健的功能表面，其中底层衬底的氧化可以忽略不计。使用X射线光电子能谱、X射线反射法和循环伏安法进行的详细表征表明，表面乙炔以中等产率反应，得到暴露二茂铁部分的表面。在制备和表征步骤期间将氧化还原活性结构广泛暴露于氧化环境后，对于由单组分1，8-壬二炔、完全乙炔化的单层制备的衍生化SAM，没有显示SiOx污染物的证据。基于诸如峰分裂和还原/氧化波的位置和形状的相关参数对所制备的Si（100）电极的氧化还原行为的分析描绘了良好的氧化还原结构，其光谱和电化学性质即使在相对于AglAgCl在-100和800 mV之间的水性介质中的延长循环之后也没有显著改变。报道的策略代表了一种实验简单的方法，用于制备硅基电极，其中，除了接近理想的氧化还原行为，可以实现显着的电极稳定性。远端炔部分的存在和高于100摄氏度的形成温度都需要实现这种表面稳定。
Here we report on the functionalization of alkyne-terminated alkyl monolayers on highly doped Si(100) using click" reactions to immobilize ferrocene derivatives. The reaction of hydrogen-terminated silicon surfaces with a diyne species was shown to afford very robust functional surfaces where the oxidation of the underlying substrate was negligible. Detailed characterization using X-ray photoelectron spectroscopy, X-ray reflectometry, and cyclic voltammetry demonstrated that the surface acetylenes had reacted in moderate yield to give surfaces exposing ferrocene moieties. Upon extensive exposure of the redox-active architecture to oxidative environments during preparative and characterization steps, no evidence of SiOx contaminants was shown for derivatized SAMs prepared from single-component 1,8-nonadiyne, fully acetylenylated, monolayers. An analysis of the redox behavior of the prepared Si(100) electrodes based on relevant parameters such as peak splitting and position and shape of the reduction/oxidation waves depicted a well-behaved redox architecture whose spectroscopic and electrochemical properties were not significantly altered even after prolonged cycling in aqueous media between -100 and 800 mV versus AglAgCl. The reported strategy represents an experimentally simple approach for the preparation of silicon-based electrodes where, in addition to close-to-ideal redox behavior, remarkable electrode stability can be achieved. Both the presence of a distal alkyne moiety and temperatures of formation above 100 degrees C were required to achieve this surface stabilization.