1. Band gap modulation in zirconium-based metal-organic frameworks by defect engineering
- Author
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Camille Petit, Davide Tiana, Michael E. A. Warwick, Matthew J. McPherson, Daniel R. Jones, Marco Taddei, and Giulia E. M. Schukraft
- Subjects
Materials science ,Band gap ,Formic acid ,chemistry.chemical_element ,02 engineering and technology ,Photochemistry ,Defect engineering ,chemistry.chemical_compound ,Rhodamine B ,General Materials Science ,MOF ,Zirconium ,Renewable Energy, Sustainability and the Environment ,Light-absorbing monocarboxylates ,Defect-engineered MOFs ,General Chemistry ,021001 nanoscience & nanotechnology ,chemistry ,UiO-66 ,Photocatalysis ,Degradation (geology) ,First principle ,Metal-organic framework ,0210 nano-technology ,Amino-functionalised benzoic acids ,Valence band energy - Abstract
We report a defect-engineering approach to modulate the band gap of zirconium-based metal-organic framework UiO-66, enabled by grafting of a range of amino-functionalised benzoic acids at defective sites. Defect engineered MOFs were obtained by both post-synthetic exchange and modulated synthesis, featuring band gap in the 4.1-3.3 eV range. Ab-initio calculations suggest that shrinking of the band gap is mainly due to an upward shift of the valence band energy, as a result of the presence of light-absorbing monocarboxylates. The photocatalytic properties of defect-engineered MOFs towards CO2 reduction to CO in the gas phase and degradation of Rhodamine B in water were tested, observing improved activity in both cases, in comparison to a defective UiO-66 bearing formic acid as the defect-compensating species.
- Published
- 2019