基于近场拉曼光谱的二氧化碳还原催化剂表界面原位表征新方法研究

Based on the latest progress of Raman spectra measurement technology and urgent need of carbon-based energy conversion research, a new method is proposed in this project for the in-situ dynamic characterization of Cu nanocrystalline catalyst during electroreductionprocess of CO2. High sensitivity, high resolution and precision measurement can be realized through a composite structure combining the tip-enhanced near-field Raman spectra measurement technology with nanocatalyzing process design. We will study the measurement principle of fiber tip-enhanced near-field Raman spectra and its optical modeling, to clarify the interaction mechanism between near field signal and the tip structure under near-field, design and optimize the fiber-probe design for near-field Raman spectra measurement. To study the fabrication method for the novel fiber probe with integration of Cu nanoelectrode, and develop a process for the controllable fabrication of the structure. To develop a measurement system for in-situ dynamic monitoring surface and interface of Cu nanocryalline catalyst under electroreduction process of CO2, and study signal extraction and analyzing method for near field Raman spectra. Experimental study will be conducted for the.catalyzing process and in-situ measurement, through chemometric modeling for predicting structure characteristics to clarify the evolution characteristics of the catalyst surface and interface structures. This study will help the understanding of the catalyzing mechanism, and impact the development of high-performance catalyst and renewable energy and carbon utilization.

基于国内外拉曼光谱测量技术的最新进展和碳基能源高效转化的科学需求，本项目拟研究一种新的原位表征方法用于二氧化碳电催化还原过程铜纳米晶催化剂表界面的动态监测。通过开发一种新的针尖增强近场拉曼光谱光纤探针和催化电极的复合结构，有望实现催化过程铜纳米晶催化剂表界面的高灵敏、高分辨率和高精度原位表征。通过研究孔径光纤探针增强的近场拉曼光谱的测量机理和光学建模，揭示近场环境下光谱信号与探针结构的相互作用机制，开发新型针尖增强近场拉曼光谱光纤探针和铜纳米晶电催化电极的复合结构设计方法和制备工艺。基于新型复合结构搭建催化剂表界面原位表征的二氧化碳电催化还原反应系统并开展催化和动态表征实验，研究近场拉曼光谱的信号测量及提取方法。通过特征拉曼光谱分析，建立化学计量模型预测催化剂表界面的演变行为，揭示铜纳米晶的催化机制。本项目研究对高效催化剂设计和碳基能源开发及碳排放固定具有重要意义。

本项目面向铜纳米结构电催化二氧化碳还原过程的机制研究开发基于近场光学测量的超快原位监测技术。通过光纤微纳米结构的探针结构巧妙设计及制备工艺探索，实现了高灵敏的近场拉曼增强探针开发。结合噪声处理及测量信号提取算法，搭建了原位测量系统，并验证了该系统可用于金属纳米结构催化过程的动态监测。 本项目为电催化过程的氧化还原机制研究提供了新方法和新工具，将促进催化过程的基础研究探索和应用技术开发。