Hierarchical Integration of Photosensitizing Metal–Organic Frameworks and Nickel‐Containing Polyoxometalates for Efficient Visible‐Light‐Driven Hydrogen Evolution. (20th April 2016)

• Record Type: Journal Article
• Authors: Kong, Xiang‐Jian; Lin, Zekai; Zhang, Zhi‐Ming; Zhang, Teng; Lin, Wenbin
• Is Part Of: Angewandte Chemie. Volume 128:Number 22(2016)
• Page Start: 6521
• Page End: 6526
• Publication Date: 2016-04-20
• Subjects: Metall-organische Gerüstverbindungen -- Photokatalyse -- Polyoxometallate -- Wasserstoffentwicklungsreaktion; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201600431
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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 (H2 O)2 (PW9 O34 )2 ] 10− (Ni4 P2 ) into two highly stable and porous phosphorescent MOFs. The proximity ofNi4 P2 to multiple photosensitizers inNi4 P2 @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 byNi4 P2 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.