Ag-M双金属改性TiO2纳米管阵列构筑及光电催化甘油产氢协同转化二羟丙酮研究

调控太阳光驱动材料结构及催化反应体系，并实现甘油重整制取氢气和二羟丙酮，是有效利用生物柴油的重要途经之一。然而，光生电子还原产氢和光生空穴氧化甘油动力学不相互匹配，制约着该技术的发展。本项目基于光电催化氧化和还原反应隔离的优势，在调控TiO2 纳米管阵列光阳极管径、管间距基础上，以化学电沉积、原位光还原法、磁控溅射等方法负载不同尺寸、形貌、配比等Ag-M双金属（M=Pt、Au、Cu等）。利用Ag-M双金属调控TiO2纳米管阵列能带结构和电子传输行为实现高效产氢，并通过调控光阳极·OH产生和甘油吸脱附协同实现甘油选择性氧化。通过吸光性、载流子分离、电子传输、·OH产生及甘油吸脱附等协同作用，构建全过程电子-空穴多路径高效转移体系，结合模拟计算，揭示Ag-M@TiO2纳米管阵列光电催化高效产氢和高选择性转化二羟丙酮的过程匹配反应机制。研究结果对于解决低附加值甘油生物质有效利用具有重要意义。

It is one of the most important routes for effective using biodiesel to reform glycerol to hydrogen and dihydroxyacetone through the regulatation of the structure of solar driving materials and the catalytic reaction system. However, the kinetics of between the photogenerated electron reduction for hydrogen production and the photogenerated hole oxidation of glycerol do not match each other, which restricts the development of this technology. Based on the isolation advantages of photoelectrochemical oxidation and reduction process, this application intend to adjust the diameter and tube spacing of the TiO2 nanotube array photoanode and load Ag-M bimetals (M = Pt, Au, Cu, etc.) with various size, morphology, ratio, composition, etc. through different methods such as chemical electrodeposition, in-situ photoreduction, magnetron sputtering, etc.. The Ag-M bimetals were used to control the band structure and electron transport behavior of TiO2 nanotube array to achieve efficient hydrogen production, and the selective oxidation of glycerol was realized by adjusting the production capacity of photoanode ·OH and glycerol adsorption-desorption ability. Through the synergistic effects of light-absorption, carrier separation, electron transport, ·OH generation, and glycerol absorption-desorption, a full-process electron-hole multi-path efficient transfer system is constructed. Finally, combined with theoretical simulation calculations, the reaction mechanism on photoelectrochemical synergistic conversion of glycerol to hydrogen and dihydroxyacetone is revealed by using the Ag-M bimetals@TiO2 nanotube array. The research results are of great significance for solving the effective application of low value-added glycerol biomass.