Taddei, Marco; Schukraft, Giulia M.; Warwick, Michael E. A.; Tiana, Davide; McPherson, Matthew J.; Jones, Daniel R.; Petit, Camille

2019

August

Journal of Materials Chemistry A

Band gap modulation in zirconium-based metal–organic frameworks by defect engineering

Validated

Altmetric: 21 ()

Band gap Zirconium UiO-66 Amino-functionalised benzoic acids MOF Defect engineering Valence band energy Light-absorbing monocarboxylates Defect-engineered MOFs

7

41

23781

23786

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.

2050-7488

http://dx.doi.org/10.1039/C9TA05216J

10.1039/C9TA05216J