Issue 35, 2020

A conductive metal–organic framework photoanode

Abstract

We report the development of photosensitizing arrays based on conductive metal–organic frameworks (MOFs) that enable light harvesting and efficient charge separation. Zn2TTFTB (TTFTB = tetrathiafulvalene tetrabenzoate) MOFs are deposited directly onto TiO2 photoanodes and structurally characterized by pXRD and EXAFS measurements. Photoinduced interfacial charge transfer dynamics are investigated by combining time-resolved THz spectroscopy and quantum dynamics simulations. Sub-600 fs electron injection into TiO2 is observed for Zn2TTFTB–TiO2 and is compared to the corresponding dynamics for TTFTB–TiO2 analogues that lack the extended MOF architecture. Rapid electron injection from the MOF into TiO2 is enhanced by facile migration of the hole away from the interfacial region. Holes migrate through strongly coupled HOMO orbitals localized on the tetrathiafulvalene cores of the columnar stacks of the MOF, whereas electrons are less easily transferred through the spiral staircase arrangement of phenyl substituents of the MOF. The reported findings suggest that conductive MOFs could be exploited as novel photosensitizing arrays in applications to slow, and thereby make difficult, photocatalytic reactions such as those required for water-splitting in artificial photosynthesis.

Graphical abstract: A conductive metal–organic framework photoanode

Supplementary files

Article information

Article type
Edge Article
Submitted
05 Aug 2020
Accepted
14 Aug 2020
First published
27 Aug 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 9593-9603

A conductive metal–organic framework photoanode

B. Pattengale, J. G. Freeze, M. J. Guberman-Pfeffer, R. Okabe, S. Ostresh, S. Chaudhuri, V. S. Batista and C. A. Schmuttenmaer, Chem. Sci., 2020, 11, 9593 DOI: 10.1039/D0SC04302H

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