Dual Regulation of Sensitizers and Cluster Catalysts in Metal-Organic Frameworks to Boost H2 Evolution

Song Guo; Chun-Wei Pan; Min Hou; Yi-Tong Hou; Shuang Yao; Tong-Bu Lu; Zhi-Ming Zhang

doi:10.1002/anie.202420398

Dual Regulation of Sensitizers and Cluster Catalysts in Metal-Organic Frameworks to Boost H2 Evolution

Angew Chem Int Ed Engl. 2024 Nov 25:e202420398. doi: 10.1002/anie.202420398. Online ahead of print.

Authors

Song Guo¹, Chun-Wei Pan¹, Min Hou¹, Yi-Tong Hou¹, Shuang Yao², Tong-Bu Lu², Zhi-Ming Zhang³

Affiliations

¹ Tianjin University of Technology, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science & Engineering, No.391 Binshuixi Road, 300384, Tianjin, CHINA.
² Tianjin University of Technology, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science & Engineering, 300384, Tianjin, CHINA.
³ Tianjin University of Technology, School of Materials Science and Engineering, No. 391 Binshuixi Road, 300384, Tianjin, CHINA.

PMID: 39586781
DOI: 10.1002/anie.202420398

Abstract

Photocatalytic efficiency is closely correlated to visible-light absorption ability, electron transfer efficiency and catalytic center activity of photocatalysts, nevertheless, the concurrent management of these factors to improve photocatalytic efficiency remains underexplored. Herein, we proposed a sensitizer/catalyst dual regulation strategy on the polyoxometalate@Metal-Organic Framework (POM@MOF) molecular platform to construct highly efficient photocatalysts. Impressively, Ni-Sb9@UiO-Ir-C6, obtained by coupling strong sensitizing [Ir(coumarin 6)2(bpy)]+ with Ni-Sb9 POM with extremely exposed nickel site [NiO3(H2O)3], can drive H2 evolution with a turnover number of 326923, representing a record value among all the POM@MOF composite photocatalysts. This performance is over 34 times higher than that of the typical Ni4P2@UiO-Ir constructed from [Ir(ppy)2(bpy)]+ and Ni4P2 POM. systematical investigations revealed that dual regulation of sensitizing and catalytic centers endowed Ni-Sb9@UiO-Ir-C6 with strong visible-light absorption, efficient inter-component electron transfer and high catalytic activity to concurrently promote H2 evolution. This work opens up a new avenue to develop highly active POM@MOF photocatalysts by dual regulation of sensitizing/catalytic centers at the molecular level.

Keywords: Hydrogen evolution; Metal-Organic Frameworks; Photocatalysis; polyoxometalate.