Release Time:2019-03-11  Hits:

Indexed by: Journal Article

Date of Publication: 2018-01-01

Journal: ACS applied materials & interfaces

Included Journals: EI、SCIE、PubMed

Volume: 10

Issue: 16

Page Number: 13462-13469

ISSN: 1944-8252

Key Words: polyoxometalate; metal-organic framework; dehydrogenation; hydrogen evolution; photocatalysis; electron transfer

Abstract: Dehydrogenation of the tetrahydroisoquinoline derivatives coupled with hydrogen production is important for hydrogen storage applications. Herein, we formulated a new system that embedded Dawson-type polyoxometalates as efficient photosensitizers into the pores of redox-active coordination polymers for the light-driven photocatalytic oxidative Mannich reaction and hydrogen evolution. In the designed Co-POM polymer, UV light excitation gives the excited state of the Dawson-type polyoxometalate first to oxidize electron donors or substrates; the reduced form (i.e., heteropolyblue) adsorbs visible light to achieve a new excited state, which reduced the cobalt redox sites and facilitates hydrogen evolution reaction. The photosensitizer recovered to the ground state, completing the catalytic cycle. Under the optimized conditions, Co-POM enabled the hydrogen evolution and dehydrogenation of tetrahydroisoquinoline without the presence of any other additives. The high catalytic efficiency and robustness indicated the advantages of the combining functional polyoxometalate-based catalysts and porous characters of the coordination polymers for the development of highly active heterogeneous catalysts.