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Understanding intrinsic light absorption properties of UiO-66 frameworks: a combined theoretical and experimental study

(2015) INORGANIC CHEMISTRY. 54(22). p.10701-10710
Author
Organization
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.
Keywords
METAL-ORGANIC FRAMEWORKS, DENSITY-FUNCTIONAL THEORY, BASIS-SET, ENERGY, PERIODIC MATERIALS, DRIVEN PHOTOCATALYST, ADSORPTION PROPERTIES, PHOTOCATALYTIC CO2 REDUCTION, EXTENDING HIRSHFELD-I, SEMICONDUCTOR PHOTOCATALYSIS

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MLA
Hendrickx, Kevin et al. “Understanding Intrinsic Light Absorption Properties of UiO-66 Frameworks: a Combined Theoretical and Experimental Study.” INORGANIC CHEMISTRY 54.22 (2015): 10701–10710. Print.
APA
Hendrickx, K., Vanpoucke, D., Leus, K., Lejaeghere, K., Van Yperen-De Deyne, A., Van Speybroeck, V., Van Der Voort, P., et al. (2015). Understanding intrinsic light absorption properties of UiO-66 frameworks: a combined theoretical and experimental study. INORGANIC CHEMISTRY, 54(22), 10701–10710.
Chicago author-date
Hendrickx, Kevin, Danny Vanpoucke, Karen Leus, Kurt Lejaeghere, Andy Van Yperen-De Deyne, Veronique Van Speybroeck, Pascal Van Der Voort, and Karen Hemelsoet. 2015. “Understanding Intrinsic Light Absorption Properties of UiO-66 Frameworks: a Combined Theoretical and Experimental Study.” Inorganic Chemistry 54 (22): 10701–10710.
Chicago author-date (all authors)
Hendrickx, Kevin, Danny Vanpoucke, Karen Leus, Kurt Lejaeghere, Andy Van Yperen-De Deyne, Veronique Van Speybroeck, Pascal Van Der Voort, and Karen Hemelsoet. 2015. “Understanding Intrinsic Light Absorption Properties of UiO-66 Frameworks: a Combined Theoretical and Experimental Study.” Inorganic Chemistry 54 (22): 10701–10710.
Vancouver
1.
Hendrickx K, Vanpoucke D, Leus K, Lejaeghere K, Van Yperen-De Deyne A, Van Speybroeck V, et al. Understanding intrinsic light absorption properties of UiO-66 frameworks: a combined theoretical and experimental study. INORGANIC CHEMISTRY. 2015;54(22):10701–10.
IEEE
[1]
K. Hendrickx et al., “Understanding intrinsic light absorption properties of UiO-66 frameworks: a combined theoretical and experimental study,” INORGANIC CHEMISTRY, vol. 54, no. 22, pp. 10701–10710, 2015.
@article{7024359,
  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.},
  author       = {Hendrickx, Kevin and Vanpoucke, Danny and Leus, Karen and Lejaeghere, Kurt and Van Yperen-De Deyne, Andy and Van Speybroeck, Veronique and Van Der Voort, Pascal and Hemelsoet, Karen},
  issn         = {0020-1669},
  journal      = {INORGANIC CHEMISTRY},
  keywords     = {METAL-ORGANIC FRAMEWORKS,DENSITY-FUNCTIONAL THEORY,BASIS-SET,ENERGY,PERIODIC MATERIALS,DRIVEN PHOTOCATALYST,ADSORPTION PROPERTIES,PHOTOCATALYTIC CO2 REDUCTION,EXTENDING HIRSHFELD-I,SEMICONDUCTOR PHOTOCATALYSIS},
  language     = {eng},
  number       = {22},
  pages        = {10701--10710},
  title        = {Understanding intrinsic light absorption properties of UiO-66 frameworks: a combined theoretical and experimental study},
  url          = {http://dx.doi.org/10.1021/acs.inorgchem.5b01593},
  volume       = {54},
  year         = {2015},
}

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