Fundamental Science and Technology of Photofunctional Interfaces

研究了TiO_2光催化剂表面产生的自由基和自由基离子及其反应中间产物的动力学行为，阐明了TiO_2光催化反应过程中产生的活性氧和有机反应中间产物以及TiO_2光催化反应过程中产生的有机自由基离子的反应性，建立了TiO_2光催化剂表面电荷分离的测定方法。TiO_2光催化反应在环境净化（污染物处理）和医疗技术方面有着广泛的应用。特别是对TiO_2光催化反应中有机物的分解机理有了重要的发现。在2001-2005财年，我们研究了基质在TiO_2表面的吸附和单电子氧化反应过程， ...更多信息 时间分辨瞬态反射测量发现，单电子氧化效率不仅与衬底的氧化电位有关，而且与衬底与TiO_2表面之间的电子相互作用有关。在2005-2007财年，我们对可见光响应型TiO_2光催化剂、气相中TiO_2光催化反应、聚氧乙烯酸盐介导的TiO_2光催化反应中的单电子氧化还原过程、β-环糊精修饰的TiO_2光催化剂空腔中有机分子的单电子氧化、以及基于瞬态吸收测量和单分子荧光成像技术的非接触式TiO_2光催化反应。结果表明，TiO_2光催化剂在光照下产生了羟基自由基和单线态氧，并在大气中分别扩散到120 μ m和2 mm。我们还研究了染料在纳米TiO_2上的吸附和电子转移过程的纳米非均匀性、活性氧的实时单分子成像和单纳米TiO_2/DNA复合物的光催化裂解，以及与太阳能电池、单分子水平的TiO_2光催化反应机理和TiO_2光催化剂的DNA复合物的关系。本研究结果对开发新型的TiO_2光催化剂和高效、高选择性的TiO_2光催化反应体系具有一定的指导意义。少

The dynamic behaviors of radicals and radical ions generated on the surface of TiO_2 photocatalyst and the reactive intermediates from the reactions of the radicals and radical ions has been studied to elucidate 1) the reactive oxygen species and organic reactive intermediates generated during the TiO_2 photocatalytic reactions and 2) reactivities of organic radical ions generated during TiO_2 photocatalytic reactions, and to develop the method for the measurement of charge separation on the surface of the TiO_2 photocatalyst. There is an application to the environmental cleanup (contaminant processing) and medical technology as application of the TiO_2 photocatalyst reaction. An important finding was especially obtained in relation to it for the decomposition mechansm of the organic compounds in the TiO_2 photocatalyst reaction. In 2001-2005 fiscal years, we studied that adsorption and one-electron oxidation reaction process of the substrate adsorbed on the TiO_2 surface based on the … More time-resolved transient reflection measurement, and found that one-election oxidation efficiency depends on not only the oxidation potential of the substrate but also the electronic interaction between the substrate and surface of TiO_2 remarkably. In 2005-2007 fiscal years, we studied visible-light responsible TiO_2 photocatalyst, TiO_2 photocatalytic reaction in gas phase, one-electron redox processes during the polyoxometalate-mediated TiO_2 photocatalytic reactions, one-electron oxidation of organic molecule included in the cavity of β-cyclodextrin modified TiO_2 photocatalyst, and non-contact TiO_2 photocatalytic reaction based on the transient absorption measurement and single molecule fluorescence imaging technique. We found that the hydroxy radical and the singlet oxygen were generated from the surface of TiO_2 by the light irradiation of the TiO_2 photocatalyst and diffuse in 120 micrometer and 2 millimeter, respectively, in the atmosphere. We also studied nanoscopic heterogeneities in ddsorption and electron transfer processes of perylene diimide dye on TiO_2 nanoparticles, real-time single-molecule imaging of the spatial and temporal distribution of reactive oxygen species, and photocatalytic cleavage of single TiO_2/DNA nanoconjugates, as relation to solar cell, TiO_2 photocatalytic reaction mechanism at single molecule level, and DNA conjugate of TiO_2 photocatalyst.. In conclusion, our results can initiate to develop new TiO_2 photocatalyst and and the TiO_2 photocatalyst reaction system with a greatly highly efficiency and high selectivities. Less