State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, MOE laboratory of Spectrochemical Analysis and Instrumentation, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China) http://bren.xmu.edu.cn.
Angew Chem Int Ed Engl. 2014 Feb 24;53(9):2353-7. doi: 10.1002/anie.201310097. Epub 2014 Jan 31.
Surface plasmon resonances (SPRs) have been found to promote chemical reactions. In most oxidative chemical reactions oxygen molecules participate and understanding of the activation mechanism of oxygen molecules is highly important. For this purpose, we applied surface-enhanced Raman spectroscopy (SERS) to find out the mechanism of SPR-assisted activation of oxygen, by using p-aminothiophenol (PATP), which undergoes a SPR-assisted selective oxidation, as a probe molecule. In this way, SPR has the dual function of activating the chemical reaction and enhancing the Raman signal of surface species. Both experiments and DFT calculations reveal that oxygen molecules were activated by accepting an electron from a metal nanoparticle under the excitation of SPR to form a strongly adsorbed oxygen molecule anion. The anion was then transformed to Au or Ag oxides or hydroxides on the surface to oxidize the surface species, which was also supported by the heating effect of the SPR. This work points to a promising new era of SPR-assisted catalytic reactions.
表面等离子体激元共振（SPRs）已被发现能促进化学反应。在大多数氧化化学反应中，氧气分子参与其中，因此理解氧气分子的活化机制非常重要。为此，我们应用表面增强拉曼光谱（SERS）来研究 SPR 辅助氧气活化的机制，使用 p-氨基苯硫酚（PATP）作为探针分子，它经历了 SPR 辅助的选择性氧化。这样，SPR 就具有了激活化学反应和增强表面物种拉曼信号的双重功能。实验和 DFT 计算都表明，在 SPR 的激发下，氧气分子通过从金属纳米颗粒中接受一个电子而被激活，形成一个强烈吸附的氧分子阴离子。然后，阴离子在表面上转化为 Au 或 Ag 的氧化物或氢氧化物，以氧化表面物种，这也得到了 SPR 加热效应的支持。这项工作预示着一个有前途的 SPR 辅助催化反应的新时代。
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