Studies on renewable two-electron reductant and oxidant aimed at water oxidation and CO2 reduction

• Project/Area Number: 26288024
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Kyoto University
• Principal Investigator: TANAKA KOJI. 京都大学, 物質ー細胞統合システム拠点, 研究員 (00029274)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000); Fiscal Year 2016: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2015: ¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000); Fiscal Year 2014: ¥8,190,000 (Direct Cost: ¥6,300,000、Indirect Cost: ¥1,890,000)
• Keywords: water oxidation / CO2 reduction / NAD/NADH model / Renewable reductant / oxyl radical complexes / Amino radical complexes / 二酸化炭素還元反応 / 再生可能有機ヒドリド試薬 / NAD/NADHモデル / 再生可能エネルギー / 再生可能有機ヒドリド / ２電子還元剤 / ２電子酸化剤 / プロトン移動と共役した電子移動 / 二酸化炭素還元 / 光化学的二酸化炭素還元

Outline of Final Research Achievements

This study is to construct NADH/NAD redox models as renewable two-electron oxidant and reductant for water oxidation and CO2 reduction. Electrochemical reduction of Ru-NADH model in CO2 saturated aqueous solutions catalytically produced HCOO-. This is the first example of catalytic CO2 reduction mediated with renewable organic hydride donor catalyst.
Ru-dioxolene frameworks exhibit very strong dπ-pπ interaction between Ru t2g and ligand π*. Deprotonation of aqua- and amino-Ru-dioxolene complexes further expands π－electron delocalization, which effectively stabilizes unusual oxyl and amino radicals. Oxidative activation of two oxyl radicals derived from dimeric aqua-Ru-dioxolen complexes resulted in O-O bond formation at the stage prior to O2 evolution in water oxidation. Oxidative activation of the anylinyl radical complex brought about intermolecular N-C bond formation through radical coupling between anilinyl radical and para-position of phenyl ring of aniline.

Research Products

• [Journal Article] Base assisted C-C coupling between carbonyl and polypyridyl ligands in Ru-NADH type carbonyl complex (2017)
  • Author(s): D. Ghosh, T. Kikuchi, K. Kobayashi, S. Kitagawa, K. Tanaka
  • Journal Title: Dalton Transactions Volume: 46 Issue: 13 Pages: 4373-4381
  • DOI: 10.1039/c7dt00312a
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Four electron reduction of new Ru-dicarbonyl complex having two NAD model ligands through decarboxylation in water (2016)
  • Author(s): Fukushima, Takashi; D. Ghosh; Kobayashi, K. Katsuaki; H. Ohtsu; S. Kitagawa; K. Tanaka,
  • Journal Title: Inorg. Chem., Volume: 55 Pages: 11613-11616
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Novel Synthesis of a Four-Electron-Reduced Ruthenium(II) NADH-Type Complex under Water-Gas-Shift Reaction Conditions, (2016)
  • Author(s): H. Ohtsu, S. Fujii, K. Tsuge, and K. Tanaka,
  • Journal Title: Dalton Trans., Volume: 45 Pages: 16130-16133
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Asymmetric Dimerization of Aniline-Ruthenium-Dioxolene Complex driven by stepwise PCET (2016)
  • Author(s): T. Kikuchi, K. Kobayashi, K. Tsuge, S. Kitagawa, K. Tanaka
  • Journal Title: Dalton Transactions Volume: 45 Issue: 36 Pages: 14030-14032
  • DOI: 10.1039/c6dt02573k
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Artificial Molecular Photosynthetic Systems: Towards Efficient Photoelectrochemical Water Oxidation (2016)
  • Author(s): Masanori Yamamoto and Koji Tanaka
  • Journal Title: ChemPlusChem Volume: 81 Issue: 10 Pages: 1028-1044
  • DOI: 10.1002/cplu.201600236
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Visible light-driven water oxidation using a covalently-linked molecular catalyst-sensitizer dyad assembled on a TiO2 electrode, (2016)
  • Author(s): Msanori Yamamoto, Lei Wang, Fusheng Li, Takashi Fukushima, Koji Tanaka, Lichen Sun, Hiroshi Imahori
  • Journal Title: Chemical Science Volume: 7 Pages: 1430-1439
  • NAID: 120005841413
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Photochemical Reduction of Low Concentrations of CO2 in a Porous Coordination Polymer with a Ruthenium(II)-CO Complex, (2016)
  • Author(s): Takashi Kajiwara, Machiko Fujii, Masahiko Tsujimo, Katsuaki Kobayashi, Masakazu Higuchi, Koji Tanaka, Susumu Kitagawa,
  • Journal Title: Angewandte Chemie, International Edition Volume: 55 Issue: 8 Pages: 2697-2700
  • DOI: 10.1002/anie.201508941
  • Peer Reviewed / Open Access
• [Journal Article] Photochemical properties and reactivity of Ru compound containing NAD/NADH functionalized 1,10-phenanthroline ligand, (2016)
  • Author(s): Katsuaki Kobayashi, Hideki Ohtsu, Koichi Nozaki, Susumu Kitagawa, Koji Tanaka,
  • Journal Title: Inorganic chemistry Volume: 55 Pages: 2076-2084
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] [RuV(NCN-Me)(bpy)(=O)]3+ Mediates Efficient C-H bond Oxidation from NADH Analogs in Aqueous Media rather than Water Oxidation (2015)
  • Author(s): Jully Patel, Karunamay Majee, Ejaz Ahma Comining, Dot Below, Koji Tanaka, Sumanta Kumar Padhi,
  • Journal Title: Dalton Trans., Volume: 44 Pages: 920-923
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Proton Induced Generation of Remote N-Heterocyclic Carbene-Ru Complexes, (2015)
  • Author(s): Takashi Fukushima, Ryoichi Fukuda, Katsuaki Kobayashi, Giovanni F. Caramori, Gernot Frenking, Masahiro Ehara, Koji Tanaka,
  • Journal Title: Chem. Eur. J., Volume: 21 Issue: 1 Pages: 106-110
  • DOI: 10.1002/chem.201490219
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Reactivity of CO2 Activated on Transition Metals and Sulfur Ligands (2015)
  • Author(s): Katsuaki Kobayashi, Koji Tanaka
  • Journal Title: Inorganic Chemistry Volume: 54 Issue: 11 Pages: 5085-5095
  • DOI: 10.1021/ic502745u
  • Peer Reviewed / Open Access
• [Journal Article] Remarkable accelerating and decelerating effects of the bases on CO2 reduction using a ruthenium NADH model complex, (2015)
  • Author(s): Hideki Ohtsu, Kiyoshi Tsuge, Koji Tanaka
  • Journal Title: Journal of Photochemistry and Photobiology A: Chemistry, Volume: 313 Pages: 163-167
  • Open Access
• [Journal Article] [RuV(NCN-Me)(bpy)(=O)]3+ Mediates Efficient C-H bond Oxidation from NADH Analogs in Aqueous Media rather than Water Oxidation (2015)
  • Author(s): Jully Patel, Karunamay Majee, Ejaz Ahma Comining, Dot Below, Koji Tanaka, Sumanta Kumar Padhi
  • Journal Title: Dlaton Trans Volume: 44 Issue: 3 Pages: 920-923
  • DOI: 10.1039/c4dt02827a
  • Peer Reviewed / Open Access
• [Journal Article] Proton Induced Generation of rNHC Ru Complex (2015)
  • Author(s): T. Fukushima, R. Fukuda, K. Kobayashi, G.F. Caramori, G. Frenking, M. Ehara
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 1 Pages: 106-110
  • DOI: 10.1002/chem.201404932
  • Peer Reviewed / Open Access
• [Journal Article] Selective Generation of Formamides through Photocatalytic CO2 Reduction Catalyzed by Ruthenium Carbonyl Compounds (2014)
  • Author(s): Katsuaki Kobayashi, Takashi Kikuchi, Susumu Kitagawa, Koji Tanaka
  • Journal Title: Angew. Chem. Int. Ed., Volume: 53 Issue: 44 Pages: 11813-11817
  • DOI: 10.1002/anie.201406553
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Reactivity of a fac-ReCl(α-diimine)(CO)3 complex with an NAD+ model ligand toward CO2 reduction, (2014)
  • Author(s): Yasuo Matsubara, Sean E. Hightower, Jinzhu Chen, David C. Grills, Dmitry E. Polyansky, James T. Muckerman, Koji Tanaka and Etsuko Fujita,
  • Journal Title: Chem. Commun Volume: 50 Issue: 6 Pages: 728-730
  • DOI: 10.1039/c3cc47699e
  • Peer Reviewed / Open Access
• [Journal Article] Water oxidation chemistry of a synthetic dinuclear ruthenium complex containing redox-active quinone ligands (2014)
  • Author(s): Isobe H, Tanaka K, Shen JR, Yamaguchi K
  • Journal Title: Inorg. Chem. Volume: 53 Issue: 8 Pages: 3973-3984
  • DOI: 10.1021/ic402340d
  • Peer Reviewed / Open Access
• [Presentation] Synthesis and characterization of Rh compound bearing NAD/NADH functionalized ligand, (2016)
  • Author(s): Katsuaki Kobayashi, Koji Tanaka
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡大学
  • Year and Date: 2016-09-10
• [Presentation] Covalent Immobilization of Ruthenium Complexes Aimed at Water Oxidation on an ITO Electrode, (2016)
  • Author(s): Takashi Fukushima, Katsuaki Kobayashi, Koji Tanaka
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡大学
  • Year and Date: 2016-09-10
• [Presentation] Base assisted unusual C-C coupling between carbonyl and polypyridyl ligands in Ru-NADH type carbonyl complex, (2016)
  • Author(s): Debashis Ghosh, Takashi Fukushima, Katsuaki Kobayashi, Koji Tanaka
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡大学
  • Year and Date: 2016-09-10
• [Presentation] Hydrogen peroxide generation using NAD/NADH functionalized Ru compounds, (2016)
  • Author(s): Katsuaki Kobayashi, Koji Tanaka
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学京田辺キャンパス
  • Year and Date: 2016-03-24
• [Presentation] 水の酸化触媒能を持つルテニウム錯体とITO電極の共有結合による複合化 (2016)
  • Author(s): 福嶋貴、小林克彰、田中晃二
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学京田辺キャンパス
  • Year and Date: 2016-03-24
• [Presentation] Proton Induced Generation of Remote N-heterocyclic Carbene-Ru Complexes, (2015)
  • Author(s): Takashi Fukushima, Katsuaki Kobayashi, Koji Tanaka
  • Organizer: PACIFICHEM2015
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2015-12-15
• [Presentation] Pathway for oxygen-oxygen bond formation and O2 release in water oxidation catalyzed by dinuclear Ru Complex, (2015)
  • Author(s): Koji Tanaka
  • Organizer: PACIFICHEM2015
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2015-12-15
  • Int'l Joint Research / Invited
• [Presentation] Photochemical property and reactivity of Ru Complexes Bearing an NAD+/NADH Functionalized Ligand (2015)
  • Author(s): Katsuaki Kobayashi, Koji Tanaka
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学
  • Year and Date: 2015-09-21
• [Presentation] Covalent Immobilization of Ruthenium Complexes Aimed at Water Oxidation on an ITO Electrode, (2015)
  • Author(s): Takashi Fukushima, Katsuaki Kobayashi, Koji Tanaka
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学
  • Year and Date: 2015-09-21
• [Presentation] 持続性社会の構築を目指した化学エネルギー変換反応の開発 (2015)
  • Author(s): 田中晃二
  • Organizer: 電気化学および境界領域の深化（電気化学会九州支部）
  • Place of Presentation: 熊本大学
  • Year and Date: 2015-04-30
  • Invited
• [Presentation] 二酸化炭素還元による炭素資源の再生 (2015)
  • Author(s): 田中晃二
  • Organizer: 第1回「二酸化炭素を原料とした物質・エネルギー変換技術研究会」
  • Place of Presentation: ホテル日航プリンセス京都
  • Year and Date: 2015-02-23
  • Invited
• [Presentation] Photo- and electrochemical CO2 reduction aimed at a C1 building block of organic materials (2014)
  • Author(s): Koji Tanaka
  • Organizer: 2014 International Conference on Artificial Photosynthesis（ICARP2014）
  • Place of Presentation: Awaji, Japan
  • Year and Date: 2014-11-24 – 2014-11-28
  • Invited
• [Presentation] NAD+/NADH 型配位子を有する新規金属錯体の合成とその性質 (2014)
  • Author(s): 藤井 翔、小林克彰、 田中晃二
  • Organizer: 第６４回錯体科学会
  • Place of Presentation: 中央大学
  • Year and Date: 2014-09-18 – 2014-09-20
• [Presentation] Ruカルボニル錯体を触媒とする光化学的CO2還元反応による選択的ホルムアミドおよびギ酸生成反応 (2014)
  • Author(s): 小林克彰、 田中晃二
  • Organizer: 第２６回配位化合物の光化学討論会
  • Place of Presentation: 首都大学東京
  • Year and Date: 2014-08-06 – 2014-08-08
• [Presentation] Radical Activation of Amine Ligands Embedded on a Ruthenium-Dioxolene Complex (2014)
  • Author(s): Takashi Kikuchi, Katuaki Kobayashi, Koji Tanaka
  • Organizer: 41st International Conference on Coordination Chemistry
  • Place of Presentation: Singapore
  • Year and Date: 2014-07-21 – 2014-07-25
• [Remarks] 第1回「二酸化炭素を原料とした物質・エネルギー変換技術研究会」
  • URL: http://www.resik.jp/newstopics/news/20150223.html