| Project/Area Number |
23K21120
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| Project/Area Number (Other) |
21H01949 (2021-2023)
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Multi-year Fund (2024)
Single-year Grants (2021-2023) |
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| Section | 一般 |
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| Review Section |
Basic Section 34010:Inorganic/coordination chemistry-related
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| Research Institution | Nagoya University |
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Principal Investigator |
CRUDDEN Cathleen 名古屋大学, トランスフォーマティブ生命分子研究所, 客員教授 (10721029)
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| Project Period (FY) |
2021-04-01 – 2025-03-31
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| Project Status |
Granted (Fiscal Year 2024)
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| Budget Amount *help |
¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000)
Fiscal Year 2024: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Fiscal Year 2023: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Fiscal Year 2022: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Fiscal Year 2021: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000)
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| Keywords | nanocluster / gold / N-heterocyclic carbene / chirality / electrocatalysis / catalysis / chiral / C-H oxidation |
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| Outline of Research at the Start |
In this proposal we will design highly active and highly selective Au nanocluster catalysts for the stereospecific oxidation of C-H bonds in complex organic molecules. Catalyst activation methods that do not result in complete degradation of the ligand sphere are critical, as are catalysts that are stable under the oxidative reaction conditions. We will take advantage of the ability to have adjacent metal atoms of the same or different oxidation states to aid in the activation, something that catalysts based on individual metal atoms lack.
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| Outline of Annual Research Achievements |
We set out to investigate whether chiral bis-benzimidazolylidene ligands based on the highly successful DIOP phosphine ligand would also generate chiral NHC-stabilized nanoclusters. We synthesized a chiral Au13 cluster stabilized by a chiral dioxolane-linked bisNHC. The resulting clusters were characterized by electrospray ionization mass spectrometry (ESI-MS), UV-vis spectroscopy, nuclear magnetic resonance (NMR) spectroscopy. We examined the CD spectra of the two enantiomers. As expected, the spectra are perfect mirror images for the two enantiomers. Unfortunately, we could not confirm the exact structure of clusters by XRD analysis, but we performed DFT calculations to explain the experimental observations and give insight into the structural details and their effects on the optical properties and chirality.
Electrochemical and thermal analyses were conducted to probe the reactivity and stability of this cluster, and its behavior as a catalyst for the electrocatalytic reduction of CO2 to CO was examined. The headspace above the reaction mixture in an H-cell was analyzed by gas chromatography equipped with a thermal conductivity detector (GC-TCD), which confirmed the production of 136 equiv of CO relative to cluster with a 74% Faradaic efficiency.
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| Current Status of Research Progress |
Current Status of Research Progress
2: Research has progressed on the whole more than it was originally planned.
Reason
We have demonstrated that employing chiral NHC-based ligands to stabilize nanoclusters offers a practical and controllable method for the preparation of highly stable, enantiopure chiral clusters. And cluster displayed high selectivity for the catalytic reduction of CO2 to CO. This result is published in Chem. Mater.
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| Strategy for Future Research Activity |
Future work will entail the synthesis of new series of gold nanoclusters by using designed NHC ligands to control size and shape of gold core. In particular, we focused on the synthesis of new heterobimetallic clusters stabilized by NHC ligands. For application to catalysis, homogeneous electrochemical investigation of NHC-gold nanoclusters will be established.
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