単一分子光水素発生デバイスの合成と機能制御

2011 年度 研究成果報告書

• 研究課題/領域番号: 21350036
• 研究種目: 基盤研究(B)
• 配分区分: 補助金
• 応募区分: 一般
• 研究分野: 無機化学
• 研究機関: 九州大学
• 研究代表者: 酒井 健 九州大学, 大学院・理学研究院, 教授 (30235105)
• 研究期間 (年度): 2009 – 2011
• キーワード: ルテニウム錯体 / 光水素発生デバイス / 光誘起電子移動 / 太陽光エネルギー変換 / 水可視光分解 / 水素エネルギー / 水素生成触媒 / 白金錯体

研究概要

太陽光エネルギーを水素エネルギーに変換するプロセスの開発を見据え、水の可視光分解反応の研究が広く行われている。本課題では、光増感能と水素生成触媒能を単分子で併せ持つ単一分子光水素発生デバイスに関して、合成と機能制御を目的とし研究を行った。その結果、デバイスの活性を制御する因子を解明することに成功し、今までに例のない、白金錯体のみで水素生成を駆動する2機能複合型光水素発生デバイスの開発にも成功した。

研究成果

• [雑誌論文] Hitoshi Sakai(1930-2008) (2012)
  • 著者名/発表者名: Ken Sakai
  • 雑誌名: Applied Geochemistry 巻: (in press)
  • URL: http://dx.doi.org/10.1016/j.apgeochem.2012.02.004
• [雑誌論文] Synthesis, crystal structure, spectroscopic and electrochemical properties, and H2-evolving activity of a new[ PtCl(terpyridine)]+ derivative with viologen-like redox properties (2012)
  • 著者名/発表者名: Masayuki Kobayashi, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Dalton Trans 巻: 41 ページ: 4903-1911
  • URL: http://dx.doi.org/10.1039/C2DT12209J
  • 査読あり
• [雑誌論文] Synthesis and characterization of self-assembled coordination polymers of N-diaminomethylene-4-(3-formyl-4-hy droxy-phenylazo)-benzenesulfonamide (2012)
  • 著者名/発表者名: Hoda El-Ghamrya, Ken Sakai, Shigeyuki Masaoka, Kamal El-Baradiea, and Raafat Issaa
  • 雑誌名: J. Coord. Chem. 巻: 65 ページ: 780-794
  • URL: http://dx.doi.org/10.1080/00958972.2012.661418
  • 査読あり
• [雑誌論文] Tuning of Redox Potentials by Introducing a Cyclometalated Bond to Bis-tridentate Ruthenium(II) Complexes Bearing Bis(Nmethylbenzimidazolyl) benzene or-pyridine Ligands (2012)
  • 著者名/発表者名: Wen-Wen Yang, Yu-Wu Zhong, Shinpei Yoshikawa, Jiang-Yang Shao, Shigeyuki Masaoka, Ken Sakai, Jiannian Yao, and Masa-aki Haga
  • 雑誌名: Inorg. Chem 巻: 51 ページ: 890-899
  • URL: http://dx.doi.org/10.1021/ic2016885
  • 査読あり
• [雑誌論文] Visible Light-induced Water Oxidation Catalyzed by Molybdenum-based Polyoxometalates with Mono-and Dicobalt(III) Cores as Oxygen-Evolving Centers (2012)
  • 著者名/発表者名: Saya Tanaka, Masahiko Annaka and Ken Sakai
  • 雑誌名: Chem. Commun 巻: 48 ページ: 1653-1655
  • URL: http://dx.doi.org/10.1039/c2cc16821a
  • 査読あり
• [雑誌論文] Self-assembly of Tubular Microstructures from Mixed-valence Metal Complexes and their Reversible Transformation via External Stimuli (2012)
  • 著者名/発表者名: Keita Kuroiwa, Masaki Yoshida, Shigeyuki Masaoka, Kenji Kaneko, Ken Sakai, and Nobuo Kimizuka
  • 雑誌名: Angew. Chem. Int. Ed 巻: 51 ページ: 656-659
  • URL: http://dx.doi.org/10.1002/anie.201105080
  • 査読あり
• [雑誌論文] Kinetics and DFT Studies on Water Oxidation by Ce4+ Catalyzed by[ Ru(terpy)(bpy)(OH2)] 2+ (2012)
  • 著者名/発表者名: Ayano Kimoto, Kosei Yamauchi, Masaki Yoshida, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Chem. Commun 巻: 48 ページ: 239-241
  • URL: http://dx.doi.org/10.1039/c1cc15109f
  • 査読あり
• [雑誌論文] Stability of Pt(II)-Based H2-Evolving Catalysts against H2 in Aqueous Solution (2011)
  • 著者名/発表者名: Kosei Yamauchi, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Dalton Trans 巻: 40 ページ: 12447-12449
  • URL: http://dx.doi.org/10.1039/c1dt11217a
  • 査読あり
• [雑誌論文] Proton-Induced Tuning of Metal-Metal Communication in Rack-Type Dinuclear Ru Complexes Containing Benzimidazolyl Moieties (2011)
  • 著者名/発表者名: Katsuaki Kobayashi, Masamichi Ishikubo, Katsuhiko Kanaizuka, Keiko Kosuge, Shigeyuki Masaoka, Ken Sakai, Koichi Nozaki, and Masa-aki Haga
  • 雑誌名: Chem. Eur. J 巻: 17 ページ: 6954-6963
  • URL: http://dx.doi.org/10.1002/chem.201100074
  • 査読あり
• [雑誌論文] Syntheses, Characterization, and Photochemical Properties of Amidate-Bridged Pt(bpy) Dimers Tethered to Ru(bpy) 32+ Derivatives (2011)
  • 著者名/発表者名: Masanari Hirahara, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Dalton Trans 巻: 40 ページ: 3967-3978
  • URL: http://dx.doi.org/10.1039/c0dt01548b
  • 査読あり
• [雑誌論文] Light-Induced Charge Separation and Photocatalytic Hydrogen Evolution from Water using RuIIPtII-Based Molecular Devices : Effects of Introducing Additional Donor and/or Acceptor Sites (2011)
  • 著者名/発表者名: Gopalakrishnan Ajayakumar, Masayuki Kobayashi, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Dalton Trans 巻: 40 ページ: 3955-3966
  • URL: http://dx.doi.org/10.1039/c0dt01673j
  • 査読あり
• [雑誌論文] Photo-Hydrogen-Evolving Molecular Devices Driving Visible-Light-Induced Water Reduction into Molecular Hydrogen : Structure-Activity Relationship and Reaction Mechanism (2011)
  • 著者名/発表者名: Hironobu Ozawa and Ken Sakai, Chem. Commun
  • 雑誌名: Chem. Commun 巻: 47 ページ: 2227-2242
  • URL: http://dx.doi.org/10.1039/c0cc04708b
  • 査読あり
• [雑誌論文] Aggregation of[ Au(CN) 4]-Anions : Detection by 15N CP-MAS NMR and the Structural Factors Influencing Intermolecular Au. N Interactions (2011)
  • 著者名/発表者名: Andrew Geisheimer, John Wren, Vladimir Michaelis, Masayuki Kobayashi, Ken Sakai
  • 雑誌名: Scott Kroeker, and Daniel Leznoff, Inorg. Chem 巻: 50 ページ: 1265-1274
  • URL: http://dx.doi.org/10.1021/ic101782v
  • 査読あり
• [雑誌論文] Platinum(II)-Based Hydrogen-Evolving Catalysts Linked to Multipendant Viologen Acceptors : Experimental and DFT Indications for Bimolecular Pathways (2011)
  • 著者名/発表者名: Makoto Ogawa, Gopalakrishnan Ajayakumar, Shigeyuki Masaoka, Heinz-Bernhard Kraatz, and Ken Sakai
  • 雑誌名: Chem. Eur. J 巻: 17 ページ: 1148-1162
  • URL: http://dx.doi.org/10.1002/chem.201002470
  • 査読あり
• [雑誌論文] Photocatalytic Hydrogen Production from Water in Self-assembled Supramolecular Iridium-cobalt Systems (2010)
  • 著者名/発表者名: Sk. Jasimuddin, Tomoko Yamada, Kazunori Fukuju, Joe Otsuki, and Ken Sakai
  • 雑誌名: Chem. Commun 巻: 46 ページ: 8466-8468
  • URL: http://dx.doi.org/10.1039/c0cc02486d
  • 査読あり
• [雑誌論文] Photochemical and Thermal Hydrogen Production from Water Catalyzed by Carboxylate-Bridged Dirhodium(II) Complexes (2010)
  • 著者名/発表者名: Saya Tanaka, Shigeyuki Masaoka, Kosei Yamauchi, Masahiko Annaka, and Ken Sakai
  • 雑誌名: Dalton Trans 巻: 39 ページ: 11218-11226
  • URL: http://dx.doi.org/10.1039/c0dt00741b
  • 査読あり
• [雑誌論文] Electrocatalytic Oxygen Evolution from Water at an ITO Electrode Modified with[ Ru(terpy){ 4, 4'-(CH_2PO_3H_2) 2-2, 2'-bpy}(OH_2)] 2+: Evidence for a Unimolecular Pathway (2010)
  • 著者名/発表者名: Josaku Kiyota, Junpei Yokoyama, Masaki Yoshida, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Chem. Lett 巻: 39 ページ: 1146-1148
  • URL: http://dx.doi.org/10.1246/cl.2010.1146
  • 査読あり
• [雑誌論文] Unprecedented Radical-Radical Reaction of a[ 2. 2] Paracyclophane Derivative Containing Imidazolyl Radical Moiety (2010)
  • 著者名/発表者名: Sayaka Hatano, Ken Sakai, and Jiro Abe
  • 雑誌名: Org. Lett 巻: 12 ページ: 4152-4155
  • URL: http://dx.doi.org/10.1021/ol1017933
  • 査読あり
• [雑誌論文] Catalysis of Mononuclear Aquaruthenium Complexes in Oxygen Evolution from Water : A New Radical Coupling Path using Hydroxocerium(IV) Species (2010)
  • 著者名/発表者名: Masaki Yoshida, Shigeyuki Masaoka, Jiro Abe, and Ken Sakai
  • 雑誌名: Chem. Asian J 巻: 5 ページ: 2369-2378
  • URL: http://dx.doi.org/10.1002/asia.201000323
  • 査読あり
• [雑誌論文] Syntheses, Characterization, and Photo-Hydrogen-Evolving Properties of Tris(2, 2'-bipyridine) ruthenium(II) Derivatives Tethered to an H2-Evolving(2-phenylpyridinato) platinum(II) Unit (2010)
  • 著者名/発表者名: Masayuki Kobayashi, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Molecules 巻: 15 ページ: 4908-4923
  • URL: http://dx.doi.org/10.3390/molecules15074908
  • 査読あり
• [雑誌論文] Frontier Orbital Engineering of Photo-Hydrogen-Evolving Molecular Devices : a Clear Relationship Between the H2-Evolving Activity and the Energy Level of the LUMO (2010)
  • 著者名/発表者名: Shigeyuki Masaoka, Yuichiro Mukawa, and Ken Sakai
  • 雑誌名: Dalton Trans 巻: 39 ページ: 5868-5876
  • URL: http://dx.doi.org/10.1039/c0dt00077a
  • 査読あり
• [雑誌論文] Photo-Hydrogen-Evolving Molecular Catalysts Consisting of Polypyridyl Ruthenium(II) Photosensitizers and Platinum(II) Catalysts : Insights into the Reaction Mechanism (2010)
  • 著者名/発表者名: Hironobu Ozawa, Masayuki Kobayashi, Bijitha Balan, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Chem. Asian J 巻: 5 ページ: 1860-1869
  • URL: http://dx.doi.org/10.1002/asia.201000083
  • 査読あり
• [雑誌論文] Photoinduced Electron Transfer in Tris(2, 2'-bipyridine) ruthenium(II)-Viol ogen Dyads with Peptide Backbones Leading to Long-Lived Charge Separation and Hydrogen Evolution (2010)
  • 著者名/発表者名: Makoto Ogawa, Bijitha Balan, Gopalakrishnan Ajayakumar, Shigeyuki Masaoka, Heinz-Bernhard Kraatz, Masayasu Muramatsu, Syoji Ito, Yutaka Nagasawa, Hiroshi Miyasaka, and Ken Sakai
  • 雑誌名: Dalton Trans 巻: 39 ページ: 4421-4434
  • URL: http://dx.doi.org/10.1039/b922689c
  • 査読あり
• [雑誌論文] Dibromido(2, 3, 9, 10-tetramethyl-1, 4, 8, 11-tetraazacyclotetradeca-1, 3, 8, 10-tet raene) cobalt(III) bromide (2009)
  • 著者名/発表者名: Hoda El-Ghamry, Raafat Issa, Kamal El-Baradie, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Acta Cryst 巻: E65 ページ: m1378-m1379
  • URL: http://dx.doi.org/10.1107/S160053680904166X
  • 査読あり
• [雑誌論文] Kinetic Resolution of P-Chirogenic Compounds by Pd-catalyzed Alcoholysis of Vinyl Ethers (2009)
  • 著者名/発表者名: Hisashi Itoh, Eiji Yamamoto, Shigeyuki Masaoka, Ken Sakai, and Makoto Tokunaga
  • 雑誌名: Adv. Synth. Cat 巻: 351 ページ: 1796-1800
  • URL: http://dx.doi.org/10.1002/adsc.200900304
  • 査読あり
• [雑誌論文] Evidence for Pt(II)-Based Molecular Catalysis in the Thermal Reduction of Water into Molecular Hydrogen (2009)
  • 著者名/発表者名: Kosei Yamauchi, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: J. Am. Chem. Soc 巻: 131 ページ: 8404-8406
  • URL: http://dx.doi.org/10.1021/ja902245e
  • 査読あり
• [雑誌論文] Oxygen Evolution from Water Catalyzed by Mononuclear Ruthenium Complexes with a Triazamacrocyclic Ligand in a Facial Fashion (2009)
  • 著者名/発表者名: Masaki Yoshida, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Chem. Lett 巻: 38 ページ: 702-703
  • URL: http://dx.doi.org/10.1246/cl.2009.702
  • 査読あり
• [雑誌論文] Hydrogen Production from Water Catalyzed by an Air-stable Di-iron Complex with a Bio-relevant Fe2(m-S) 2 Core (2009)
  • 著者名/発表者名: Toshiki Yamaguchi, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Chem. Lett 巻: 38 ページ: 434-435
  • URL: http://dx.doi.org/10.1246/cl.2009.434
  • 査読あり
• [雑誌論文] Bis(2, 2'-bipyridine){ ethyl4'-[ N-(4-carbamoylphenyl) carbamoyl]-2, 2'-bipy ridine-4-carboxylate} ruthenium(II) bis[ hexafluoridophosphate(V)] (2009)
  • 著者名/発表者名: Masanari Hirahara, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Acta Cryst 巻: E65 ページ: m228-m229
  • URL: http://dx.doi.org/10.1107/s1600536809002360
  • 査読あり
• [雑誌論文] Synthesis, Crystal Structure, Solution and Spectroscopic Properties, and Hydrogen-Evolving Activity of[ K(18-Crown-6)][ Pt(II)(2-phenylpyridi nato) Cl2] (2009)
  • 著者名/発表者名: Masayuki Kobayashi, Shigeyuki Masaoka, and Ken Sakai
  • 雑誌名: Photobiol. Sci 巻: 8 ページ: 196-203
  • URL: http://dx.doi.org/10.1039/b814939a
  • 査読あり
• [学会発表] Charge Storage over Multiviologen Tethers and Application to Pt(II)-Catalyzed Hydrogen Evolution from Water (2011)
  • 著者名/発表者名: Ken Sakai
  • 学会等名: The 3rd Asian Conference on Coordination Chemistry(ACCC-3), the India Habitat Centre
  • 発表場所: New Delhi, India
  • 年月日: 20111017-20
• [学会発表] Photoinduced Charge Storage in Supramolecular Photocatalysts with Multiviologen Tethers and Applications to Hydrogen Evolution from Water (2011)
  • 著者名/発表者名: Ken Sakai
  • 学会等名: The 94th Canadian Chemistry Conference and Exhibition in Montreal
  • 発表場所: Montreal, Canada
  • 年月日: 20110605-09
• [学会発表] RuPt-based Photo-hydrogen-evolving Molecular Devices towards the Development of Artificial Photosynthesis (2011)
  • 著者名/発表者名: Ken Sakai
  • 学会等名: The 94th Canadian Chemistry Conference and Exhibition in Montreal
  • 発表場所: Montreal, Canada
  • 年月日: 20110605-09
• [学会発表] Photoinduced Charge Storage in Multipendant Viologen Tethers Leading to Hydrogen Evolution from Water Catalyzed by Platinum(II) Complexes (2010)
  • 著者名/発表者名: Ken Sakai
  • 学会等名: 11^(th) Eurasia Conference on Chemical Sciences
  • 発表場所: The Dead Sea, Jordan
  • 年月日: 20101006-10
• [学会発表] Photoinduced Hydrogen Evolution from Water Driven by Pt(II)-Based Molecular Photocatalysts (2010)
  • 著者名/発表者名: Ken Sakai
  • 学会等名: Inaugural(1st) International Conference on Molecular and Functional Catalysis
  • 発表場所: Resort Worlds Sentosa, Singapore
  • 年月日: 20100711-15
• [学会発表] Toward the Development of Artificial Photosynthesis Generating Hydrogen Energy from Water and Sunlight (2010)
  • 著者名/発表者名: Ken Sakai
  • 学会等名: the 2010 International Chemical Congress of Pacific Basin Societies(Pacifichem 2010)
  • 発表場所: Honolulu, Hawaii, USA
  • 年月日: 2010-10-19
• [学会発表] Hydrogen Production from Water using the Pt(II)-Based Molecular Catalysts (2010)
  • 著者名/発表者名: Ken Sakai
  • 学会等名: the 2010 International Chemical Congress of Pacific Basin Societies(Pacifichem 2010)
  • 発表場所: Honolulu, Hawaii, USA
  • 年月日: 2010-10-15
• [学会発表] "Hydrogen Production from Water Catalyzed by Bio-relevant and Non-bio-relevant Multinuclear Metal Complexes (2009)
  • 著者名/発表者名: Ken Sakai
  • 学会等名: ICBIC 14, Nagoya Congress Center
  • 発表場所: Nagoya, Japan
  • 年月日: 20090725-30
• [学会発表] Photo-Hydrogen-Evolving Molecular Devices Consisting of Tris(2, 2'-bipyridine) ruthenium(II)-bas ed Photosensitizers and Pt(II)-based Molecular Catalysts (2009)
  • 著者名/発表者名: Ken Sakai
  • 学会等名: 2nd ACCC, Jinling Riverside Conference Hotel
  • 発表場所: Nanjing, China
  • 年月日: 2009-11-03
• [学会発表] Tris(2, 2'-bipyridine) ruthenium(II)-bas ed Photo-hydrogen-evolving Molecular Devices Using Platinum(II)-based Hydrogenic Activation (2009)
  • 著者名/発表者名: Ken Sakai
  • 学会等名: 18th ISPPCC, Gateaux Kingdom Sapporo
  • 発表場所: Sapporo, Japan
  • 年月日: 2009-07-05
• [図書] 機能材料1月号特集人工光合成 (2012)
  • 著者名/発表者名: 山内幸正、酒井健
  • 総ページ数: 38-46
  • 出版者: シーエムシー
• [図書] 有機合成化学協会誌 (2011)
  • 著者名/発表者名: 吉田将己、正岡重行、酒井健
  • 総ページ数: 370-378
  • 出版者: 社団法人有機合成化学協会
• [図書] 人工光合成と有機系太陽電池 (2011)
  • 著者名/発表者名: 小澤弘宜、酒井健、化学同人
  • 総ページ数: 88-95
  • 出版者: 化学同人
• [図書] 単一分子光水素発生デバイスの化学 (2009)
  • 著者名/発表者名: 正岡重行、小林真之、酒井健
  • 総ページ数: 118-121
  • 出版者: 光化学協会
• [図書] 配位空間の化学 (2009)
  • 著者名/発表者名: 酒井健, 北川進
  • 総ページ数: 214-222
  • 出版者: シーエムシー
• [備考]
  • URL: http://www.scc.kyushu-u.ac.jp/Sakutai/
• [産業財産権] 白金多核錯体触媒およびそれを用いた人工光合成方法 (2011)
  • 発明者名: 酒井健・今野陽介・正岡重行
  • 権利者名: 九州大学
  • 産業財産権番号: 特許、PCT/JP2011/78480
  • 出願年月日: 2011-12-08
  • 外国
• [産業財産権] 白金多核錯体触媒およびそれを用いた人工光合成方法 (2010)
  • 発明者名: 酒井健・今野陽介・正岡重行
  • 権利者名: 九州大学
  • 産業財産権番号: 特許、特願2010-273727
  • 出願年月日: 2010-12-08
• [産業財産権] 新規有機配位子、キレート錯体および多電子貯蔵型光電荷分離分子装置 (2010)
  • 発明者名: 酒井健・小川誠
  • 権利者名: 九州大学
  • 産業財産権番号: 特許、特願2010-151367
  • 出願年月日: 2010-07-01