Understanding Intrinsic Light Absorption Properties of UiO-66 Frameworks: A Combined Theoretical and Experimental Study

Kevin Hendrickx, Danny E. P. Vanpoucke, Karen Leus, Kurt Lejaeghere, Andy Van Yperen-De Deyne, Veronique Van Speybroeck*, Pascal Van Der Voort, Karen Hemelsoet

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

110 Citations (Web of Science)

Abstract

A combined theoretical and experimental study is performed in order to elucidate the effects of linker functional groups on the photoabsorption properties of UiO-66-X materials. This study, in which both mono- and difunctionalized linkers (with X = OH, NH2, or SH) are investigated, aims to obtain a more complete picture of the choice of functionalization. Static time-dependent density functional theory calculations combined with molecular dynamics simulations are performed on the linkers, and the results are compared to experimental UV/vis spectra in order to understand the electronic effects governing the absorption spectra. The disubstituted linkers show larger shifts than the monosubstituted variants, making them promising candidates for further study as photocatalysts. Next, the interaction between the linker and the inorganic part of the framework is theoretically investigated using a cluster model. The proposed ligand-to-metal-charge transfer is theoretically observed and is influenced by the differences in fundtionalization. Finally, the computed electronic properties of the periodic UiO-66 materials reveal that the band gap can be altered by linker functionalization and ranges from 4.0 down to 2.2 eV. Study of the periodic density of states allows the band gap modulations of the framework to be explained in terms of a functionalization-induced band in the band gap of the original UiO-66 host.

Original languageEnglish
Pages (from-to)10701-10710
Number of pages10
JournalInorganic Chemistry
Volume54
Issue number22
DOIs
Publication statusPublished - 16 Nov 2015
Externally publishedYes

Keywords

  • METAL-ORGANIC FRAMEWORKS
  • PHOTOCATALYTIC CO2 REDUCTION
  • EXTENDING HIRSHFELD-I
  • BASIS-SET
  • ENERGY
  • NANOPARTICLES
  • ADSORPTION
  • OXIDATION
  • EFFICIENT
  • WATER

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