Journal
JOURNAL OF MATERIALS CHEMISTRY A
Volume 7, Issue 41, Pages 23781-23786Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9ta05216j
Keywords
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Funding
- European Union's Horizon 2020 Research and Innovation Programme under the Marie Sklodowska-Curie grant [663830]
- Engineering and Physical Sciences Research Council (EPSRC) [EP/R01910X/1, EP/L015277/1]
- University of Edinburgh
- EPSRC [EP/P020267/1, EP/M028267/1]
- ERDF through the Welsh Government [80708]
- Ser Solar project via the Welsh Government
- EPSRC [EP/P020267/1, EP/R01910X/1, EP/M028267/1] Funding Source: UKRI
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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. First principle calculations suggest that shrinking of the band gap is likely 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.
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