Fundamental Science and Technology of Photofunctional Interfaces

光功能界面基础科学与技术

• 批准号: 14050055
• 负责人: MAJIMA Tetsuro
• 金额: $ 53.63万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14050055/
• 关键词: TiO_2 Photocatalyst; One-electron oxidation; Radicalion; Transient absorption measurement; Signle molecule spectroscopy; Singlet oxygen; Hydroxyl radical; TiO_2 Photocatalytic reaction mechanism; TiO_2光触媒反応; 光機能界面; ラジカルカチオン; -電子酸化; -電子還元; 過渡吸

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

研究了自由基和自由基离子在TiO_2光催化剂表面生成的自由基和自由基离子及其反应中间体的动力学行为，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体以及TiO_2光催化反应过程中产生的有机自由基离子的反应活性。开发了TiO_2光催化剂表面电荷分离的测量方法。TiO_2光催化反应在环境净化（污染物处理）和医疗技术中有应用前景。在TiO_2光催化反应中，有机化合物的分解机理得到了重要的发现。在2001-2005财政年度，我们基于时间分辨瞬态反射测量研究了吸附在TiO_2表面的衬底的吸附和单电子氧化反应过程，发现一次选择氧化效率不仅取决于衬底的氧化势，还显著取决于衬底与TiO_2表面之间的电子相互作用。在2005-2007财政年度，我们研究了可见光作用下的TiO_2光催化剂，气相TiO_2光催化反应，多金属氧酸盐介导的TiO_2光催化反应中的单电子氧化还原过程，β-环糊精修饰TiO_2光催化剂腔内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TiO_2光催化反应。结果表明，TiO_2在光催化剂的照射下，表面产生羟基自由基，单线态氧在大气中扩散，分别在120微米和2毫米范围内扩散。我们还研究了苝二亚胺染料在TiO_2纳米粒子上的吸附和电子转移过程的纳米异质性，实时单分子成像的活性氧的时空分布，光催化裂解单个TiO_2/DNA纳米缀合物与太阳能电池的关系，TiO_2光催化反应的单分子机制，以及TiO_2光催化剂的DNA缀合物。综上所述，我们的研究结果为开发新型TiO_2光催化剂和高效、高选择性的TiO_2光催化剂反应体系奠定了基础。少

项目成果

Transient Absorption Spectra and Lifetimes of Ketyl Radicals in the Excited State

激发态羰基自由基的瞬态吸收光谱和寿命

• 发表时间: 2004
• 期刊: J. Phys. Chem. A (Lett. ) 108(40)
• 作者: 立川貴士;真嶋哲朗;T. Tachikawa;K. Naito;T. Tachikawa;M. Sakamoto;X. Cai;M. Sakamoto;X. Cai;M. Sakamoto;Masanori Sakamoto;Kiyohiko Kawai;Mamoru Fujitsuka;Michihiro Hara;Takashi Tachikawa;Yosuke Oseki;Shingo Samori;Takashi Tachikawa;Yosuke Oseki;Kazuya Naito;Masanori Sakamoto;Mamoru Fujitsuka;Masanori Sakamoto;Xichen Cai;Masanori Sakamoto;Michihiro Hara;Takumi Kimura;Shinro Yasui;Shingo Samori;Michihiro Hara;Shingo Samori;Masayuki Endo;Koji Nakayama;Kiyohiko Kawai;Masayuki Endo;Masayuki Endo;Kimio Akiyama;Masayuki Endo;Takashi Tachikawa;Tadao Takada;Xichen Cai;Kiyohiko Kawai;Takahiro Kawai;Xichen Cai;Kiyohiko Kawai;Takashi Tachikawa;Kiyohiko Kawai;Kiyohiko Kawai;Mamoru Fujitsuka;Michihiro Hara;Takashi Tachikawa;Masanori Sakamoto;Shingo Samori;Kiyohiko Kawai;Kiyohiko Kawai;Tadao Takada;Masanori Sakamoto;Mamoru Fujitsuka;T. Tachikawa;T. Tachikawa;T. Tachikawa;T. Tachikawa;T. Tachikawa;T. Tachikawa;s. Tojo;S. Tojo;T. Tachikawa;T. Tachikawa;X. Cai;M. Sakamoto;X. Cai;M. Sakamoto;T. Tachikawa;T. Tachikawa;T. Tachikawa;T. Tachikawa;T. Tachikawa;S. Tojo;S. Tojo;T. Tachikawa;X. Cai;M. Sakamoto;M. Sakamoto
• 通讯作者: M. Sakamoto

Stepwise Photocleavage of Two C-O Bonds of 1,8-Bis[(4-benzoylphenoxy)-methyl]naphthalene with Three-Step Excitation Using Three-Color Three-Lacer Flash Photolysis

使用三色三点闪光光解三步激发逐步光裂解 1,8-双[(4-苯甲酰基苯氧基)-甲基]萘的两个 C-O 键

• 发表时间: 2004
• 期刊: J.Am.Chem.Soc.(Commun.) 126
• 作者: 立川貴士;真嶋哲朗;T. Tachikawa;K. Naito;T. Tachikawa;M. Sakamoto;X. Cai;M. Sakamoto;X. Cai;M. Sakamoto;Masanori Sakamoto;Kiyohiko Kawai;Mamoru Fujitsuka;Michihiro Hara;Takashi Tachikawa;Yosuke Oseki;Shingo Samori;Takashi Tachikawa;Yosuke Oseki;Kazuya Naito;Masanori Sakamoto;Mamoru Fujitsuka;Masanori Sakamoto;Xichen Cai;Masanori Sakamoto;Michihiro Hara;Takumi Kimura;Shinro Yasui;Shingo Samori;Michihiro Hara;Shingo Samori;Masayuki Endo;Koji Nakayama;Kiyohiko Kawai;Masayuki Endo;Masayuki Endo;Kimio Akiyama;Masayuki Endo;Takashi Tachikawa;Tadao Takada;Xichen Cai;Kiyohiko Kawai;Takahiro Kawai;Xichen Cai;Kiyohiko Kawai;Takashi Tachikawa;Kiyohiko Kawai;Kiyohiko Kawai;Mamoru Fujitsuka;Michihiro Hara;Takashi Tachikawa;Masanori Sakamoto;Shingo Samori;Kiyohiko Kawai;Kiyohiko Kawai;Tadao Takada;Masanori Sakamoto;Mamoru Fujitsuka;T. Tachikawa;T. Tachikawa;T. Tachikawa;T. Tachikawa;T. Tachikawa;T. Tachikawa;s. Tojo;S. Tojo;T. Tachikawa;T. Tachikawa;X. Cai;M. Sakamoto;X. Cai;M. Sakamoto;T. Tachikawa;T. Tachikawa;T. Tachikawa;T. Tachikawa;T. Tachikawa;S. Tojo;S. Tojo;T. Tachikawa;X. Cai;M. Sakamoto;M. Sakamoto;Tadao Takada;Tadao Takada;Xichen Cai
• 通讯作者: Xichen Cai

Kiyohiko Kawai: "Two-color two-laser damaging DNA"Angew.Chem.Int.Ed.Eng.. (in press). (2004)

Kiyohiko Kawai：“双色双激光损伤 DNA”Angew.Chem.Int.Ed.Eng..（正在出版）。

T.Takada, K.Kawai, S.Tojo, T.Majima: "Hole Transfer in DNA : DNA as a Scaffold for Hole Transfer between Two Organic Molecules"Tetrahedron Lett..

T.Takada、K.Kawai、S.Tojo、T.Majima：“DNA 中的空穴转移：DNA 作为两个有机分子之间空穴转移的支架”Tetrahedron Lett..

Mechanistic Insight into theTiO_2 Photocatalystic Reactions : Design of New Photocatalysts

TiO_2 光催化反应的机理洞察：新型光催化剂的设计

• 发表时间: 2007
• 期刊: J. Phys. Chem、 C 111(14)
• 作者: T. Tachikawa