| 研究課題/領域番号 |
23K21120
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| 補助金の研究課題番号 |
21H01949 (2021-2023)
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| 研究種目 |
基盤研究(B)
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| 配分区分 | 基金 (2024)
補助金 (2021-2023) |
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| 応募区分 | 一般 |
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| 審査区分 |
小区分34010:無機・錯体化学関連
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| 研究機関 | 名古屋大学 |
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研究代表者 |
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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| 研究期間 (年度) |
2021-04-01 – 2025-03-31
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| 研究課題ステータス |
交付 (2024年度)
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| 配分額 *注記 |
17,550千円 (直接経費: 13,500千円、間接経費: 4,050千円)
2024年度: 3,120千円 (直接経費: 2,400千円、間接経費: 720千円)
2023年度: 3,120千円 (直接経費: 2,400千円、間接経費: 720千円)
2022年度: 3,380千円 (直接経費: 2,600千円、間接経費: 780千円)
2021年度: 7,930千円 (直接経費: 6,100千円、間接経費: 1,830千円)
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| キーワード | nanocluster / gold / N-heterocyclic carbene / chirality / electrocatalysis / catalysis / chiral / C-H oxidation |
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| 研究開始時の研究の概要 |
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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| 研究実績の概要 |
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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| 現在までの達成度 (区分) |
現在までの達成度 (区分)
2: おおむね順調に進展している
理由
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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| 今後の研究の推進方策 |
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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