Dicopper Dioxygenase Model Immobilized in Mesoporous Silica Nanoparticles for Toluene Oxidation: A Mechanism to Harness Both O Atoms of O2 for Catalysis

Chih Cheng Liu, Yi Fang Tsai, Chung Yuan Mou, Steve S.F. Yu, Sunney I. Chan

研究成果: 雜誌貢獻文章同行評審

3 引文 斯高帕斯(Scopus)

摘要

Recently, we have reported on a dicopper system (CuIII(μ-O)2CuIII complex immobilized in mesoporous silica nanoparticles) that can mediate the catalytic conversion of toluene into benzaldehyde by O2, in which the oxidizing power of both O atoms is harnessed for catalytic turnover. This is the first example of a CuIII(μ-O)2CuIII complex capable of functioning like a "dioxygenase" in hydrocarbon oxidation. We have undertaken a mechanistic study to clarify how this catalytic conversion is accomplished without the input of sacrificial reductants. While the first O atom in the CuIII(μ-O)2CuIII complex can actively insert into a C-H bond, the second O atom left in the CuII(μ-O)CuII complex is inert. We show that a second molecule of O2 is involved in activating the dicopper catalyst, forming an O2 complex with the CuII(μ-O)CuII intermediate to give a species with the [Cu2O3]2+ core, which then mediates the transfer of the remaining O atom of the original O2 molecule to the organic substrate to complete the catalytic turnover. The study offers a mechanistically characterized analogue of the heterogeneous metal oxide catalyst that oxidizes organic substrates with the lattice oxygens by the Mars-van-Krevelen (MvK) mechanism at significantly higher temperatures.

原文英語
頁(從 - 到)11032-11043
頁數12
期刊Journal of Physical Chemistry C
123
發行號17
DOIs
出版狀態已發佈 - 5月 2 2019
對外發佈

ASJC Scopus subject areas

  • 電子、光磁材料
  • 能源(全部)
  • 物理與理論化學
  • 表面、塗料和薄膜

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