Zhan Chao, Wang Zi-Yuan, Zhang Xia-Guang, Chen Xue-Jiao, Huang Yi-Fan, Hu Shu, Li Jian-Feng, Wu De-Yin, Moskovits Martin, Tian Zhong-Qun
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering , Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Xiamen University , Xiamen 361005 , China.
Department of Chemistry , University of California, Santa Barbara , Santa Barbara , California 93106 , United States.
J Am Chem Soc. 2019 May 22;141(20):8053-8057. doi: 10.1021/jacs.9b02518. Epub 2019 May 13.
Surface plasmons (SPs) are able to promote chemical reactions through the participation of the energetic charge carriers produced following plasmons decay. Using p-aminothiophenol (PATP) as a probe molecule, we used surface-enhanced Raman spectroscopy to follow the progress of its transformation, in situ, to investigate systematically the role of hot electrons and holes. The energetic carrier mediated PATP oxidation was found to occur even in the absence of oxygen, and was greatly influenced by the interface region near the gold surface. The observed reaction, which occurred efficiently on Au@TiO nanostructures, did not happen on bare gold nanoparticles (NPs) or core-shell nanostructures when a silicon oxide layer blocked access to the gold. Moreover, the product of the PATP oxidation with oxygen on Au@TiO nanostructures differed from what was obtained without oxygen, suggesting that the mechanism through which "hot holes" mediated the oxidation reaction was different from that operating with oxygen activated by hot electrons.
表面等离子体激元（SPs）能够通过参与等离子体激元衰变后产生的高能电荷载流子来促进化学反应。我们以对氨基硫酚（PATP）作为探针分子，利用表面增强拉曼光谱原位跟踪其转化过程，以系统研究热电子和热空穴的作用。结果发现，即使在无氧条件下，高能载流子介导的PATP氧化反应也会发生，并且该反应受到金表面附近界面区域的极大影响。观察到的反应在Au@TiO纳米结构上高效发生，但当氧化硅层阻止与金接触时，在裸金纳米颗粒（NPs）或核壳纳米结构上则不会发生。此外，Au@TiO纳米结构上PATP与氧气发生氧化反应的产物与无氧条件下得到的产物不同，这表明“热空穴”介导氧化反应的机制与热电子激活氧气的机制不同。
