Creation of New Chemistry for Energy Conversion from pH gradients

利用 pH 梯度创建能量转换新化学

• 批准号: 12440190
• 负责人: TANAKA Koji
• 金额: $ 9.86万
• 依托单位: Institute for Molecular Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440190/
• 关键词: Aqua-RU complex; Oxo-Ru complex; Oxyl radical; dioxygen evolution; energy conversion; pH gradients; エネルギー変換; 酸化反応; 水の4電子酸化; オキソ金属錯体

Aqua-Ru-quinone complexes, [Ru(trpy)(Q)(OH_2)]^<2+>, dissociate proton to give[Ru(trpy)(Q)(OH^-)]^+ with anionic hydroxy group or [Ru(trpy)(SQ)(HO^-)]+ with hydroxy radical, that is produced by intramolecular electron transfer from hydroxy anion to quinone. Dissociation of hydroxy proton of [Ru(trpy)(Q)(OH^-)]^+ also intramolecula electron transfer from the resultant oxy1 dianion ot quinone. We have successfully isolated [Ru(trpy)(SQ)(O^-)]^0 and determinined the molecular structure of the first Ru-oxo complex with oxyl radical. The fact that Ru-O bound distance of the oxyl radicla complexes is close to that of Ru-OH_2 bond indicates that the multi-bond character is not so high in the Ru-O bond. The Ru-oxo complex with oxyl radicla has essentially no ability to oxidize organic compounds, but one-electron oxidized form of the complex abstract hydrogen atoms of cyclic diens. Compared with monomeric Ru-oxo complexes, dinuclear Ru-oxo one showed high reactivity for hydrogen abstraction of cyclic dienes upon two electron oxidation of the complex. Moreover, the dinuclear complex showed high catalytic ability for four-electron oxidation of water, and the turnover number of dioxygen was 35000 based on the complex. Thus, we succeeded energy conversion from pH gradients to electricity, and also oxidation of not only organic compounds but also water by using unique redox behavior of aqua-Ru-dioxolene complexes.

水-Ru-苯二酚配合物[Ru(Trpy)(Q)(OH_2)]^&lt；2+&gt；与阴离子羟基反应生成[Ru(Trpy)(Q)(OH^-)]^+或[Ru(Trpy)(Sq)(Ho^-)]+与羟基自由基反应，通过分子内电子转移反应生成。[Ru(Trpy)(Q)(OH^-)]^+的羟质子的解离也从生成的氧-1-二阴离子转移到分子内的电子转移。我们成功地分离了[Ru(Trpy)(Sq)(O^-)]^0，并测定了第一个含氧自由基的Ru-oxo配合物的分子结构。氧自由基络合物的Ru-O键距与Ru-OH_2键的键距相近，说明Ru-O键的多键性质不是很高。含氧基的Ru-oxo络合物基本上不具有氧化有机化合物的能力，而是环状二烯的络合物抽象氢原子的单电子被氧化的形式。与单体Ru-oxo络合物相比，双核Ru-oxo-one对环二烯在络合物两电子氧化反应中具有较高的吸氢活性。此外，该双核配合物对水的四电子氧化表现出很强的催化能力，氧的周转数为35000。因此，我们成功地利用水-Ru-二恶烯络合物独特的氧化还原行为，实现了从pH梯度到电性的能量转换，不仅可以氧化有机化合物，还可以氧化水。

项目成果

K.TsugemK, Kurihara, K.Tanaka: "Energy Conversion from Proton Gtradient to Electricity Based on Characteristic Redox Behavior of an Aqua Ruthenium with a WQuinone Ligand"Bulletin of Chemical Society of Japan. 73. 607-614 (2000)

K.TsugemK、Kurihara、K.Tanaka：“基于水钌与 WQuinone 配体的特征氧化还原行为从质子梯度到电能的能量转换”日本化学会通报。

T. Wada, K. Tsuge and K. Tanaka: "Synthesis and Redox Properties of Bis(ruthenium-hydroxo)complexe with Quinone and Bipyridine Ligand as a Water-Oxidation Catalysts"Inorg. Chem. 40. 329 (2001)

T. Wada、K. Tsuge 和 K. Tanaka：“作为水氧化催化剂的双（钌-羟基）配合物与醌和联吡啶配体的合成和氧化还原性质”Inorg。

T.Wada, K.Tsuge, K.Tanaka: "Synthesis and Redox Propertics of Bis(ruthenium-hydroxo)complexes with Quinone and Bipyridine Ligand as Water-Oxidation Catalysis"Inorganic Chemistry. 40. 329-335 (2001)

T.Wada、K.Tsuge、K.Tanaka：“作为水氧化催化作用的双（钌-羟基）配合物与醌和联吡啶配体的合成和氧化还原性质”无机化学。

Kaname Ito, Toshi Nagata, Koji Tanaka: "Synthesis and Electrochemical Properties of Transition Metal Complexes of 2,2':6',2"-Terpyridine 1,1 "-Dioxide,"Inorg. Chein. 40. 6331-6333 (2001)

Kaname Ito、Toshi Nagata、Koji Tanaka：“2,2:6,2”-三联吡啶 1,1“-二氧化物的过渡金属配合物的合成和电化学性质，”Inorg。

T.Wada, K.Tsuge, K.Tanaka: "Synthesis and Redox Properties of Bis(ruthenium-hydroxo)complexes with Quinone and Bipyridine Ligand as a Water-Oxidation Catalysts"Inorganic Chemistry. 40. 329-335 (2001)

T.Wada、K.Tsuge、K.Tanaka：“作为水氧化催化剂的双（钌-羟基）配合物与醌和联吡啶配体的合成和氧化还原性质”无机化学。