Cluster (spacecraft)

Organic chemistry

Metal-organic framework

Photocatalysis

Visible spectrum

Electron transfer

Radical

Adsorption

Engineering

Catalysis

Inorganic chemistry

Chemistry

Materials science

Programming language

Computer science

Metal

Chemical engineering

Optoelectronics

Redox

Photochemistry

Oxidizing agent

Journal of the American Chemical Society

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 O2•- 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.

Turning on Visible-Light Photocatalytic C−H Oxidation over Metal–Organic Frameworks by Introducing Metal-to-Cluster Charge Transfer