Turning on Visible-Light Photocatalytic C-H Oxidation over Metal-Organic Frameworks by Introducing Metal-to-Cluster Charge Transfer.
J Am Chem Soc
; 141(48): 19110-19117, 2019 Dec 04.
Article
em En
| MEDLINE
| ID: mdl-31707780
ABSTRACT
The tailorable structure and electronic structure of metal-organic frameworks (MOFs) greatly facilitate their modulated light harvesting, redox power, and consequently photocatalysis. Herein, a representative MOF, UiO-66, was furnished by installing Fe3+ onto the Zr-oxo clusters, to give Fe-UiO-66, which features extended visible light harvesting, based on metal-to-cluster charge transfer (MCCT). The Fe-UiO-66 with unique electronic structure and strong oxidizing power exhibits visible light-driven water oxidation, which is impossible for pristine UiO-66. More strikingly, under visible irradiation, the generated holes over Fe-UiO-66 are able to exclusively convert H2O to hydroxide radicals, initiating and driving the activation of stubborn C-H bond, such as toluene oxidation. The electrons reduce O2 to O2â¢- radicals that further promote the oxidation reaction. The related catalytic mechanism and the structure-activity relationship have been investigated in detail. As far as we know, this is not only an unprecedented report on activating "inert" MOFs for photocatalytic C-H activation but also the first work on extended light harvesting and enhanced photocatalysis for MOFs by introducing an MCCT process.
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01-internacional
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MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2019
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Article