Practically modified attenuated total reflection surface-enhanced IR absorption spectroscopy for high-quality frequency-extended detection of surface species at electrodes.
Practically modified attenuated total reflection surface-enhanced IR absorption spectroscopy for high-quality frequency-extended detection of surface species at electrodes.
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DOI：
10.1021/ac7017487
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发表时间：
2008
影响因子：
7.4
通讯作者：
Xiao-Kang Xue;Jin-yi Wang;Qiaoxia Li;Yan-Gang Yan-Yan-Gang-Yan-93057829;Jian-Hua Liu;W. Cai
中科院分区：
文献类型：
--
作者：
Xiao-Kang Xue;Jin-yi Wang;Qiaoxia Li;Yan-Gang Yan-Yan-Gang-Yan-93057829;Jian-Hua Liu;W. Cai
本文提出了一种改进的ATR结构，即在半圆柱形ZnSe棱镜和硅片之间加入一个亲水夹层作为集成窗口，用于原位电化学表面增强红外吸收光谱（SEIRAS）。这种新的ATR光学器件显著提高了有效红外光束通过ZnSe/gap/Si/金属薄膜的吞吐量，能够在更大的入射角下容易地检测到低至700 cm（-1）的高质量光谱指纹，而不会影响沉积在Si上的金属薄膜的电化学可行性和稳定性。利用这种改进的ATR-SEIRAS技术的优点，对两个选定的体系进行了初步探索：宽范围的原位ATR-SEIRAS光谱为酸性溶液中甲醇在Pt电极上的电氧化提供了甲酸盐中间体途径的有力证据;此外，本发明还涉及一种用于该方法，新的光谱指纹揭示了全面的取向信息的p-在Pt电极上的硝基苯甲酸物种作为结果的解离吸附的对硝基苯甲酸分子从酸溶液。
A practically modified ATR configuration has been proposed for in situ electrochemical surface-enhanced IR absorption spectroscopy (SEIRAS) by sandwiching an ultrathin water interlayer between a hemicylindrical ZnSe prism and a Si wafer as an integrated window. This new ATR optics significantly enhances the throughput of an effective IR beam across the ZnSe/gap/Si/metal film, enabling high-quality spectral fingerprints down to 700 cm(-1) to be readily detected at larger incidence angles without compromising the electrochemical feasibility and stability of metallic films deposited on Si. The advantages of this modified ATR-SEIRAS have been initially applied to explore two selected systems: wide-ranged in situ ATR-SEIRA spectra provided strong evidence in support of the formate intermediate pathway for methanol electrooxidation at the Pt electrode in an acid solution; in addition, new spectral fingerprints revealed comprehensive orientational information about of the p-nitrobenzoate species at Pt electrode as a result of the dissociative adsorption of p-nitrobenzoic acid molecules from an acid solution.