Activation of Oxygen on Gold and Silver Nanoparticles Assisted by Surface Plasmon Resonances**
Activation of Oxygen on Gold and Silver Nanoparticles Assisted by Surface Plasmon Resonances**
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表面等离子共振辅助金银纳米粒子上的氧活化
DOI：
10.1002/anie.201310097
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发表时间：
2014-02-24
影响因子：
16.6
通讯作者：
Tian, Zhong-Qun
中科院分区：
文献类型：
--
作者：
Huang, Yi-Fan;Zhang, Meng;Tian, Zhong-Qun
表面等离子体共振(SPR)被发现可以促进化学反应。在大多数氧化化学反应中，氧分子都参与其中，了解氧分子的活化机理是非常重要的。为此，我们利用表面增强拉曼光谱(SERS)，以SPR辅助选择氧化的对氨基硫酚(PATP)为探针分子，研究了SPR辅助氧活化的机理。因此，SPR具有激活化学反应和增强表面物种拉曼信号的双重功能。实验和密度泛函理论计算都表明，在表面等离子体共振的激发下，氧分子通过接受金属纳米粒子上的电子而被激活，形成强吸附的氧分子阴离子。然后，阴离子在表面转化为金或银的氧化物或氢氧化物，以氧化表面物种，这也得到了SPR的加热效应的支持。这项工作预示着SPR辅助催化反应的一个很有前途的新时代。
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.