基于Au-Pd氢溢流制备黑色TiO2纳米线及光催化苯甲醇无溶剂氧化性能研究

In this project, black TiO2 nanowires were prepared by the hydrogen spillover from Au-Pd bimetallic nanoparticles to TiO2, and photogenerated electrons and holes from black TiO2 nanowires were used to activate benzyl alcohol and O2, realizing low temperature photocatalytic solvent-free oxidation of benzyl alcohol to produce benzaldehyde. More special emphasis will be laid on investigating the mechanism for preparing black TiO2 base on the hydrogen spillover, and explore the unique surface structure (disordered surface and oxygen vacancies) of black TiO2 nanowires to expand the photoelectrochemical response region and improve charge transport and charge separation; Furthermore, the activation mechanism of benzyl alcohol and O2 molecules by the photogenerated electrons and holes will be discussed, and the synergistic effect among black TiO2 disordered surface, oxygen vacancies and noble metal in photocatalytic reaction and the reaction mechanism for the solvent-free photocatalytic oxidation of benzyl alcohol will be also revealed. Besides, the ideas and methods of this project will promote technological innovation in the field of preparing structure-sensitive photocatalysts, and also will give direction for developing highly active catalysts in the photocatalytic oxidation of various alcohols to produce more functional compounds.

本项目研究基于Au-Pd双金属-载体间氢溢流还原制备具有光转化效率高的黑色TiO2纳米线，并研究利用光激发黑色TiO2纳米线产生的电子-空穴对低温活化苯甲醇及O2分子，实现低温光催化苯甲醇无溶剂氧化制备苯甲醛。项目重点研究基于氢溢流的黑色TiO2纳米线还原制备机理，揭示黑色TiO2纳米线表面结构与性质的低温可控制备规律，并探索利用其独特的表面结构(不规则外表层、氧空缺位等)拓展其对太阳光响应范围，增强分离、转移电子-空缺对的能力，进而提高光转化效率；认识电子-空穴对活化苯甲醇及O2分子的作用规律，获得黑色TiO2不规则外表层、氧空缺位及Au-Pd双金属在光催化反应中协同效应，以及光催化苯甲醇氧化反应机理。本项目思想和方法将促进结构敏感型光催化剂制备领域的技术创新，为进一步开发高活性催化剂光催化各种醇类氧化制备更多功能化合物奠定基础。

本研究项目揭示基于贵金属（包括Au、Ag、Pd、Pt及其合金等）表面氢溢流还原制备具有光转化效率高的“黑色”TiO2纳米材料及其表面结构性质调控规律，探明了利用其独特的表面结构增强其对太阳光响应范围以及增强分离、转移电子-空缺对的能力，基本认识了电子-空穴对活化苯甲醇及O2分子的作用规律，获得了黑色TiO2及贵金属在光催化反应中协同效应，实现了低温光催化苯甲醇无溶剂氧化制备苯甲醛；基本掌握高效的低温光催化苯甲醇无溶剂氧化黑色TiO2纳米线催化剂结构与性能间的关系，项目研究成果将促进结构敏感型光催化剂制备领域的技术创新，在有机化合物的绿色高效光催化合成以及环境方面有机污染物处理等方面具有广泛的的应用前景。