化学学报 ›› 2014, Vol. 72 ›› Issue (11): 1125-1138.DOI: 10.6023/A14080602 上一篇    下一篇

综述

对氨基苯硫酚分子的表面增强拉曼光谱及等离激元光催化反应

赵刘斌a, 黄逸凡a, 吴德印a, 任斌a,b   

  1. a 厦门大学化学化工学院固体表面物理化学国家重点实验室 厦门 361005;
    b 厦门大学能源材料协同创新中心 厦门 361005
  • 投稿日期:2014-08-25 发布日期:2014-10-17
  • 通讯作者: 吴德印, 任斌 E-mail:bren@xmu.edu.cn;dywu@xmu.edu.cn
  • 作者简介:赵刘斌,男,厦门大学化学化工学院,2014年获厦门大学博士学位,现为西南大学讲师,主要研究方向为表面增强拉曼光谱理论和金属纳米结构表面光电化学反应理论.黄逸凡,男,2013年获厦门大学博士学位,现为荷兰莱顿大学博士后.主要研究方向电化学表界面光谱.吴德印,男,厦门大学化学化工学院教授,博士生导师,主要研究方向为表面增强拉曼光谱理论、电荷转移和传输理论、分子光谱理论.任斌,男,厦门大学化学化工学院教授,博士生导师,主要研究方向为光谱电化学、电催化、电分析、表面等离激元光子学、纳米电化学、纳米电分析、纳米材料合成.

Surface-enhanced Raman Spectroscopy and Plasmon-Assisted Photocatalysis of p-Aminothiophenol

Zhao Liubina, Huang Yifana, Wu Deyina, Ren Bina,b   

  1. a State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005;
    b Innovation Center of Chemistry for Energetic Materials, Xiamen University, Xiamen 361005
  • Received:2014-08-25 Published:2014-10-17

对氨基苯硫酚(PATP)是表面增强拉曼光谱(SERS)研究中最重要的探针分子之一. PATP吸附体系具有非常特征且异常强的SERS信号, 但人们对其SERS信号的理解仍存在较大争议. 本文结合文献, 总结了我们为了理解PATP分子异常的SERS光谱所开展的系统的理论和实验工作. 首先介绍PATP的SERS增强机理方面开展的理论工作, 研究表明PATP分子的异常SERS信号不是来自PATP分子本身, 而是来自其表面催化偶联反应产物二巯基偶氮苯(DMAB). 通过实验和DMAB合成两个方面, 验证了DMAB是异常SERS信号的根源. 其次总结了各种实验条件对PATP转化为DMAB的影响, 并从实验和理论两个角度探讨PATP的表面催化偶联反应机理. 最后, 通过对PATP体系的SERS和等离激元增强化学反应的总结, 展望表面等离激元增强化学反应的未来发展方向.

关键词: 对氨基苯硫酚(PATP), 表面增强拉曼光谱, 表面等离激元共振, 光催化反应, 密度泛函理论

p-Aminothiophenol (PATP) is one of the most important probe molecules in surface-enhanced Raman spectroscopy (SERS). Adsorbed PATP exhibits very unique and abnormally intense SERS signals. However, the understanding toward the abnormal SERS signals is still in debate. In this review, we overview our theoretical and experimental studies to understand the abnormal SERS of PATP. We first introduce the theoretical investigation on the SERS enhancement mechanism of PATP. The theoretical study shows that the abnormal SERS signals of PATP are not from PATP itself but arise from its surface catalytic coupling product p,p'-dimercaptoazobenzene (DMAB). The assumption is supported by carefully designed experiments of PATP and the SERS signal of the synthesized DMAB molecule. Then, we summarize the experimental factors that influence the photochemical conversion of PATP to DMAB on the surfaces of metal nanostructures. We then explore the reaction mechanisms for the surface catalytic coupling reaction of PATP in both experimental and theoretical aspects. Finally, we proposed the further direction of surface plasmon enhanced chemical reaction on the basis of our systematically studies of SERS and plasmon photocatalysis of PATP.

Key words: p-aminothiophenol (PATP), surface-enhanced Raman spectroscopy, surface plasmon resonance, photocatalysis, density functional theory