Photoinduced hydrogen evolution with highly functional photocatalyst

高功能光催化剂光诱导析氢

• 批准号: 06453100
• 负责人: OKURA Ichiro
• 金额: $ 2.05万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453100/
• 关键词: Intramolecular electron transfer; Porphyrin; Viologen; Laser flash photolysis; Photoinduced hydrogen evolution; Hydrogenase; レーザーフッラシュ

Various viologen linked porphyrins have been synthesized, which provide photosensitizer and electron carrier in the same molecule.Porphyrin containing viologen with different numbers of methylene groups were synthesized and used for photoinduced intramolecular electron transfer.The fluorescence decay profiles consist of the sum of two first order decays with two lifetimes. The long fluorescence lifetimes of the viologen linked porphyrins are almost the same as the lifetime of the porphyrin without viologen. It is reasonable to assume that the fluorescence decay of the component with a long lifetime is spontaneous and is therefore independent of the distance between the viologen and the porphyrin ring. In contrast, the shorter lifetime strongly depends on the length of the methylene chain and the value increases with longer chain lengths. Therefore the fluorescence decay of the component with the short lifetime may arise from the direct quenching of the photoexcited singlet state of the porphyrin by the linked viologen.The intramolecular electron transfer rate constant strongly depends on the methylene chain length and it decreases with increasing methylene chain length. In the intramolecular electron transfer process, the electron transfers from the photoexcited porphyrin to the viologen along the methylene chain. Photoinduced hydrogen evolution was accomplished with the viologen-linked porphyrin by the irradiation of visible light.

合成了不同亚甲基数目的紫精连接卟啉，并将其用于光诱导的分子内电子转移，荧光衰减曲线由两个一级衰减和两个寿命组成。紫精连接的卟啉的长荧光寿命几乎与没有紫精的卟啉的寿命相同。可以合理地假设，具有长寿命的组分的荧光衰减是自发的，因此与紫精和卟啉环之间的距离无关。相反，较短的寿命强烈依赖于亚甲基链的长度，并且该值随着链长而增加。因此，短寿命组分的荧光衰减可能是由于连接紫精直接猝灭卟啉的光激发单重态引起的。分子内电子转移速率常数强烈依赖于亚甲基链长，并随亚甲基链长的增加而减小。在分子内电子转移过程中，电子从光激发的卟啉沿沿着亚甲基链转移到紫精上。紫精连接卟啉在可见光照射下实现光诱导析氢。

项目成果

Y.Amao and I.Okura: "Effect of cationic surfactant on photoinduced hydrogen evolution with hydrogenase" J.Mol.Catal., A : Chemistry. 103. 69-71 (1995)

Y.Amao 和 I.Okura：“阳离子表面活性剂对氢化酶光致析氢的影响”J.Mol.Catal.，A：化学。

J.Hirota andI.Okura: "Photoinduced intramolecular electron transfer in bisbiologen-linked porphyrin" Porphyrins. 3. 383-388 (1995)

J.Hirota 和 I.Okura：“双生物素连接的卟啉中的光诱导分子内电子转移”卟啉。

Y. Amao and I. Okura: "Effect of cationic surfactant on photoinduced hydrogen evolution with hydrogenase" J. Mol. Catal., A: Chemistry. 103. 69-71 (1995)

Y. Amao 和 I. Okura：“阳离子表面活性剂对氢化酶光致析氢的影响”J. Mol。

S.Aono, A.Ohtaka, and I.Okura: "The effect of chemical modification of zinc myoglobin on the photoinduced electron transfer with methyl viologen" J.Mol.Catal.A : Chem.96. 87-92 (1995)

S.Aono、A.Ohtaka 和 I.Okura：“锌肌红蛋白的化学修饰对甲基紫精光诱导电子转移的影响”J.Mol.Catal.A：Chem.96。

S. Aono, A. Ohtaka, and I. Okura: "The effect of chemical modificaiton of zinc myoglogin on the photoinduced electron transfer with methylviologen" J. Mol. Catal., A: Chemistry. 87-92 (1995)

S. Aono、A. Ohtaka 和 I. Okura：“锌肌登录素化学修饰对甲基紫精光诱导电子转移的影响”J. Mol。