| Project/Area Number |
16072204
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | The University of Tokyo |
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Principal Investigator |
IWASAWA Yasuhiro The University of Tokyo, Department of Chemistry, Professor (40018015)
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| Co-Investigator(Kenkyū-buntansha) |
MU Xindong The University of Tokyo, Department of Chemistry, Assinstant Professor (20422363)
NOMURA Masaharu High Energy Accelerator Research Organization, Institute of Materials Structure Science Photon Factory, Professor (70156230)
佐々木 岳彦 東京大学, 大学院・新領域創成科学研究科, 助教授 (90242099)
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| Project Period (FY) |
2004 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥104,700,000 (Direct Cost: ¥104,700,000)
Fiscal Year 2006: ¥29,000,000 (Direct Cost: ¥29,000,000)
Fiscal Year 2005: ¥47,400,000 (Direct Cost: ¥47,400,000)
Fiscal Year 2004: ¥28,300,000 (Direct Cost: ¥28,300,000)
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| Keywords | Catalyst surface / X-ray a bsorption fine structure(XAFS) / Time-resolved XAFS / Scanning tunneling microscope(STM) / Direct phenol synthesis / Photo-oxidation catalysis / Catalytic reaction meachanism / In situ characterization / X線吸収微細構造 / 選択酸化 / In-situ解析 / 触媒 / 表面 / 分子構造 / ダイナミクス / 触媒作用 / SPM / XAFS / 時間分解構造解析 / DXAFS / 可視光反応 / TiO2 / セリア-ジルコニア固溶体 / ヒドロホルミル化 / 光触媒 |
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| Research Abstract |
We studied the catalytically active structure, its structural transformation and dynamics, and reaction mechanism for direct phenol synthesis from benzene and molecular oxygen on a novel N-interstitial Re_<10>-cluster catalyst supported on HZSM-5 zeolite, which exhibited remarkable performances for the direct phenol synthesis. The active N-interstitial Re_<10> cluster was produced by NH_3 and it was the active species for the direct phenol synthesis using O_2 as an oxidant. Molecular oxygen (O_2) was suggested to directly react with benzene without dissociation to atomic oxygen (Ea (activation energy) = 24 kJ mol^<-1>) and the active Re cluster dynamically converted to inactive Re monomers under the reaction conditions. The structural transformation between the Re cluster and the Re monomers cycled during the phenol synthesis, whose mechanism was studied by in-situ time-resolved XAFS techniques.
TiO_2 is a typical functional metal oxide which exhibits photocatalysis. Usually only ultraviolet light must be used for photochemical reactions on TiO_2 because of its bulk band gap. However, we discovered visible light photo-oxidation reactions of formic acid on the ordered lattice-work structure of a TiO_2(001) surface by using scanning tunneling microscopy (STM). Two photon photoelectron and electron energy loss spectroscopies and density functional theory calculations revealed that the nanostructured surface makes the band gap significantly smaller than 3.0 eV only at the surface layer and that the surface state of the crystal enables visible light response.
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