2019 Fiscal Year Final Research Report
Reduction of Carbon Dioxide to Methanol Using Heterometal-doped Copper Hydride Clusters
| Project/Area Number |
18K14243
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| Research Category |
Grant-in-Aid for Early-Career Scientists
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| Allocation Type | Multi-year Fund |
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| Review Section |
Basic Section 34010:Inorganic/coordination chemistry-related
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| Research Institution | Nara Women's University |
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Principal Investigator |
Nakamae Kanako 奈良女子大学, 自然科学系, 助教 (20757231)
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| Project Period (FY) |
2018-04-01 – 2020-03-31
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| Keywords | 銅ヒドリド / 金属クラスター / 貴金属代替材料 / 二酸化炭素 / ホスフィン / 水素化触媒 / ナノ分子 |
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| Outline of Final Research Achievements |
By using a linear tetraphosphine, meso‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm), nona‐ and hexadecanuclear copper hydride clusters, [Cu9H7(μ‐dpmppm)3]2+ and [Cu16H14(μ‐dpmppm)4]2+ were synthesized and characterized. They form copper‐hydride cages of apex‐truncated supertetrahedral {Cu9H7}2+ and square‐face‐capped cuboctahedral {Cu16H14}2+ structures. The hydride positions were estimated by DFT calculations to be facially dispersed around the copper frameworks. A kinetically controlled synthesis gave an unsymmetrical Cu8H6 cluster, [Cu8H6(μ‐dpmppm)3]2+, which readily reacted with CO2 to afford linear Cu4 complexes with formate bridges, leading to an unprecedented hydrogenation of CO2 into formate catalyzed by {Cu4(μ‐dpmppm)2} platform. The results demonstrate that new motifs of copper hydride clusters could be established by the tetraphosphine ligands, and the structures influence their reactivity.
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| Free Research Field |
化学
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| Academic Significance and Societal Importance of the Research Achievements |
本課題は，原子を操りモノづくりを行う立場から元素戦略を提案するものでもあり，分子レベルの設計に基づく安価な卑金属を用いた貴金属代替材料開発を目指した。今回開発した銅ヒドリドクラスターは，いらない二酸化炭素から有用物質への変換の仲介役を務めるものとして重要で，さらに，複数の金属イオン間で起こる反応の分子としての解析は，不均一系触媒表面上のモデルとなり，機構解明への知見を与えるものと期待される。本研究は，水素と化学エネルギーの供給が依然課題として残ってはいるものの，ギ酸やメタノールなどを中心に維持可能な循環型物質社会の構築を目指す学際的に不可欠な取り組みへの一翼を担うものと位置づけられよう。
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