Hierarchical Integration of Photosensitizing Metal-Organic Frameworks and Nickel-Containing Polyoxometalates for Efficient Visible-Light-Driven Hydrogen Evolution

Metal–organic frameworks (MOFs) provide a tunable platform for hierarchically integrating multiple components to effect synergistic functions that cannot be achieved in solution. Here we report the encapsulation of a Ni‐containing polyoxometalate (POM) [Ni4(H2O)2(PW9O34)2]10− (Ni4P2) into two highly...

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Bibliographic Details
Published in:Angewandte Chemie (International ed.) 2016-05, Vol.55 (22), p.6411-6416
Main Authors: Kong, Xiang-Jian, Lin, Zekai, Zhang, Zhi-Ming, Zhang, Teng, Lin, Wenbin
Format: Article
Language:English
Subjects:
Catalysts
Catalytic activity
Electrochemistry
Electron transfer
Encapsulation
Evolution
Hydrogen
hydrogen evolution reaction
Hydrogen evolution reactions
Integration
Metal-organic frameworks
Metals
Nickel
Phosphorescence
Photocatalysis
Photosensitization
polyoxometalate
Polyoxometallates
Proximity
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Summary:Metal–organic frameworks (MOFs) provide a tunable platform for hierarchically integrating multiple components to effect synergistic functions that cannot be achieved in solution. Here we report the encapsulation of a Ni‐containing polyoxometalate (POM) [Ni4(H2O)2(PW9O34)2]10− (Ni4P2) into two highly stable and porous phosphorescent MOFs. The proximity of Ni4P2 to multiple photosensitizers in Ni4P2@MOF allows for facile multi‐electron transfer to enable efficient visible‐light‐driven hydrogen evolution reaction (HER) with turnover numbers as high as 1476. Photophysical and electrochemical studies established the oxidative quenching of the excited photosensitizer by Ni4P2 as the initiating step of HER and explained the drastic catalytic activity difference of the two POM@MOFs. Our work shows that POM@MOF assemblies not only provide a tunable platform for designing highly effective photocatalytic HER catalysts but also facilitate detailed mechanistic understanding of HER processes. POM & MOF work hand in hand: A tetra‐nickel‐containing polyoxometalate (POM) was encapsulated into the pores of phosphorescent metal–organic frameworks (MOFs). The hierarchical POM@MOF assemblies effect highly efficient photocatalytic hydrogen evolution reactions through facile multielectron transfer processes.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201600431