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Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis

Hamad, S., Hernandez, N. C., Aziz, A., Ruiz-Salvador, A. R., Calero, S. and Grau-Crespo, R. (2015) Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis. Journal of Materials Chemistry A, 3 (46). pp. 23458-23465. ISSN 0959-9428

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To link to this item DOI: 10.1039/C5TA06982C

Abstract/Summary

Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:44373
Uncontrolled Keywords:Metal-organic frameworks, porphyrin, photocatalysis, density functional theory
Publisher:Royal Society of Chemistry

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