In situ SHINERS at electrochemical single-crystal electrode/electrolyte interfaces: tuning preparation strategies and selected applications.
In situ SHINERS at electrochemical single-crystal electrode/electrolyte interfaces: tuning preparation strategies and selected applications.
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DOI：
10.1021/nn403444j
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发表时间：
2013-09
期刊：
影响因子：
17.1
通讯作者：
Jian-feng Li;A. Rudnev;Yongchun Fu;Nataraju Bodappa;T. Wandlowski
中科院分区：
文献类型：
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作者：
Jian-feng Li;A. Rudnev;Yongchun Fu;Nataraju Bodappa;T. Wandlowski
我们用电化学方法和原位壳层隔离纳米粒子增强拉曼光谱研究了金和铂两种低折射率单晶电极上的Au(55 Nm)@SiO_2纳米粒子(NPs)。我们发现了由合成的发光剂NPs所产生的表面活性剂对电极的封闭作用。我们介绍了一种解决这一问题的有效方法，这为闪光剂在表面电化学和其他领域的应用提供了一个基础平台。我们的方法是基于闪光NP修饰的单晶表面的放氢处理。在Au(Hkl)和Pt1(Hkl)上的电位控制吸附和相形成的电化学闪光实验中证明了我们的制备策略的可靠性。我们在这些定义明确、结构精细的单晶表面上获得了高质量的拉曼光谱。对特征A1振动模的分析与单晶伏安法和计时电流法实验的解释完全一致。我们的研究表明，在这项工作中开发的Shiners协议使这种拉曼方法成为一种开创性的方法，具有在明确定义的电化学固/液界面上进行原位结构和反应性研究的独特机会。
We have studied Au(55 nm)@SiO2 nanoparticles (NPs) on two low-index phases of gold and platinum single crystal electrodes in ClO4(-) and SO4(2-) ion-containing electrolytes by both electrochemical methods and in-situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS). We showed the blocking of the electrode with surfactants originating from the synthesis of as-prepared SHINERS NPs. We introduce an efficient procedure to overcome this problem, which provides a fundamental platform for the application of SHINERS in surface electrochemistry and beyond. Our method is based on a hydrogen evolution treatment of the SHINERS-NP-modified single-crystal surfaces. The reliability of our preparation strategy is demonstrated in electrochemical SHINERS experiments on the potential-controlled adsorption and phase formation of pyridine on Au(hkl) and Pt(hkl). We obtained high-quality Raman spectra on these well-defined and structurally carefully characterized single-crystal surfaces. The analysis of the characteristic A1 vibrational modes revealed perfect agreement with the interpretation of single-crystal voltammetric and chronoamperometric experiments. Our study demonstrates that the SHINERS protocol developed in this work qualifies this Raman method as a pioneering approach with unique opportunities for in situ structure and reactivity studies at well-defined electrochemical solid/liquid interfaces.