Electron Injection from Photoexcited Metal-Organic Framework Ligands to Ru2 Secondary Building Units for Visible-Light-Driven Hydrogen Evolution

Guangxu Lan; Yuan-Yuan Zhu; Samuel S Veroneau; Ziwan Xu; Daniel Micheroni; Wenbin Lin

doi:10.1021/jacs.8b01601

Electron Injection from Photoexcited Metal-Organic Framework Ligands to Ru₂ Secondary Building Units for Visible-Light-Driven Hydrogen Evolution

J Am Chem Soc. 2018 Apr 25;140(16):5326-5329. doi: 10.1021/jacs.8b01601. Epub 2018 Apr 3.

Authors

Guangxu Lan¹, Yuan-Yuan Zhu^{1

2}, Samuel S Veroneau¹, Ziwan Xu^{1

3}, Daniel Micheroni¹, Wenbin Lin¹

Affiliations

¹ Department of Chemistry , The University of Chicago , 929 E 57th Street , Chicago , Illinois 60637 , United States.
² School of Chemistry and Chemical Engineering , Hefei University of Technology , Hefei 230009 , China.
³ College of Chemistry and Molecular Engineering , Peking University , Beijing 100871 , China.

PMID: 29578703
DOI: 10.1021/jacs.8b01601

Abstract

We report the design of two new metal-organic frameworks (MOFs), Ru-TBP and Ru-TBP-Zn, based on Ru₂ secondary building units (SBUs) and porphyrin-derived tetracarboxylate ligands. The proximity of Ru₂ SBUs to porphyrin ligands (∼1.1 nm) facilitates multielectron transfer from excited porphyrins to Ru₂ SBUs to enable efficient visible-light-driven hydrogen evolution reaction (HER) in neutral water. Photophysical and electrochemical studies revealed oxidative quenching of excited porphyrin by Ru₂ SBUs as the initial step of the HER process and the energetics of key intermediates in the catalytic cycle. Our work provides a new strategy to building multifunctional MOFs with synergistic ligands and SBUs for efficient photocatalysis.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.