RT Journal Article
T1 Engineering the electronic and optical properties of 2D porphyrin-paddlewheel metal-organic frameworks
A1 Posligua, V.
A1 Pandya, D.
A1 Aziz, A.
A1 Rivera, M.
A1 Otero, R. C.
A1 Hamad, Said
A1 Grau-Crespo, R.
K1 Machine Learning
K1 Metal-Organic Frameworks
K1 Solar fuels
AB 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 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.
PB IOP Publishing Ltd
YR 2021
FD 2021
LK https://hdl.handle.net/10433/22981
UL https://hdl.handle.net/10433/22981
LA en
NO J. Phys. Energy 3 034005
NO Departamento de Sistemas Físicos, Químicos y Naturales
DS RIO
RD Apr 23, 2026