Engineering the electronic and optical properties of 2D porphyrin paddlewheel metal-organic frameworks

Posligua, V., Pandya, D., Aziz, A., Rivera, M., Crespo-Otero, R., Hamad, S. and Grau-Crespo, R. ORCID: https://orcid.org/0000-0001-8845-1719 (2021) Engineering the electronic and optical properties of 2D porphyrin paddlewheel metal-organic frameworks. Journal of Physics: Energy, 3 (3). 034005. ISSN 2515-7655 doi: 10.1088/2515-7655/abeab4

Abstract/Summary

Metal organic frameworks (MOFs) are promising photocatalytic materials due to their high surface area and tuneability of their electronic structure. We discuss here how to engineer the band structures and optical properties of a family of two-dimensional (2D) porphyrin-based MOFs, consisting of M tetrakis(4 carboxyphenyl) porphyrin structures (M TCPP, where M = Zn or Co) and metal (Co, Ni, Cu or Zn) paddlewheel clusters, with the aim of optimising their photocatalytic behaviour in solar fuel synthesis reactions (water splitting and/or CO2 reduction). Based on density functional theory (DFT) and time-dependent DFT simulations with a hybrid functional, we studied three types of composition/structural modifications: a) varying the metal centre at the paddlewheel or at the porphyrin centre to modify the band alignment; b) partially reducing the porphyrin unit to chlorin, which leads to stronger absorption of visible light; and c) substituting the benzene bridging between the porphyrin and paddlewheel, by ethyne or butadiyne bridges, with the aim of modifying the linker to metal charge transfer behaviour. Our work offers new insights on how to improve the photocatalytic behaviour of porphyrin- and paddlewheel-based MOFs.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/98245
Item Type	Article
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Uncontrolled Keywords	metal organic frameworks, photocatalysis, porphyrins, density functional theory
Publisher	Institute of Physics
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