金属基异质结构垂直阵列构筑及其电催化过程的原位SERS检测研究

Electrocatalysis plays an important role in clean energy technology in the future, but the complex catalytic mechanism becomes the bottleneck of developing high efficiency electrocatalysis. SERS has shown great potential in the in situ study of electrocatalysis due to its fast and high resolution properties, but its applicability to the widely used semiconductor electrocatalysis system is poor at present. To address this key scientific question, this project intends to use the photoelectric characteristics of the vertical array of metal-based heterostructure to construct the model of electrocatalyst and improve the current in situ SERS technology parallel used for in situ detection and mechanism research of the electrocatalytic process.It mainly includes: Preparation of in vertical arrays of metal-based heterostructure, and selection of high efficiency model electrocatalysts; Studying the basic rules when vertical arrays of metal-based heterostructures used for SERS bases, and developing SERS bases suitable for electrocatalytic systems that semiconductor involved; Using model catalyst and efficient SERS bases jointly to realize in situ detection of electrocatalytic process and elucidation of its mechanism. The research results of this project will lay a theoretical and experimental foundation for the development of high-efficiency electrocatalysts and semiconductor-oriented SERS bases, as well as the revelation of energy conversion mechanism of electrocatalysis and biological systems.

电催化在未来清洁能源技术中占有重要地位，但复杂的催化机理成为开发高效电催化剂的瓶颈。SERS以其快速、高分辨等特性在电催化原位研究中显示出巨大潜力，但对应用广泛的半导体电催化体系适用性差。针对这一关键科学问题，本项目拟利用金属基异质结构垂直阵列的光电特性，构筑模型电催化剂与适用于半导体的高效SERS基底，并联用于电催化过程的原位检测与机理研究。主要包括：制备金属基异质结构垂直阵列，并遴选高效模型电催化剂；研究金属基异质结构垂直阵列用以SERS基底时的基本作用规律，开发适用于半导体电催化体系的SERS基底；联用模型催化剂与高效SERS基底实现对电催化过程的原位检测，阐明其机理。本项目的研究成果对于开发高效电催化剂与面向半导体的高效SERS基底，以及揭示电催化、生物等体系的能量转换机理奠定理论与实验基础。

原位拉曼光谱检测在电催化、环境监测、医疗检测、食品卫生安全等领域应用日益广泛。但是，适用于半导体拉曼光谱检测的高效基底在理论与实践上仍缺少突破。本项目从表面增强拉曼光谱的物理与化学增强机理出发，将长程SPP与短程LSPR效应相结合，并通过驻极体促进金属@半导体拉曼基底与吸附分子极化水平的方法来提高半导体表面的拉曼光谱的检测能力；同时，我们发现对于有机污染物，在驻极体的强大电场极化作用下，其分子电极化率改变较大，拉曼增强效果明显，特别是以驻极体为载体的纳米银三角@二维半导体材料的复合结构，拉曼增强效果明显，因此有望将本方法应用于土壤与水体的痕量有机污染物检测；而且，开发合适的经济半导体激光器可增强有机物在红外光区的拉曼光谱，进一步提高检测水平与适用范围。