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The remarkable amphoteric nature of defective UiO-66 in catalytic reactions

(2017) CHEMCATCHEM. 9(12). p.2203-2210
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Abstract
One of the major requirements in solid acid and base catalyzed reactions is that the reactants, intermediates or activated complexes cooperate with several functions of catalyst support. In this work the remarkable bifunctional behavior of the defective UiO-66(Zr) metal organic framework is shown for acid-base pair catalysis. The active site relies on the presence of coordinatively unsaturated zirconium sites, which may be tuned by removing framework linkers and by removal of water from the inorganic bricks using a dehydration treatment. To elucidate the amphoteric nature of defective UiO-66, the Oppenauer oxidation of primary alcohols has been theoretically investigated using density functional theory (DFT) and the periodic approach. The presence of acid and basic centers within molecular distances is shown to be crucial for determining the catalytic activity of the material. Hydrated and dehydrated bricks have a distinct influence on the acidity and basicity of the active sites. In any case both functions need to cooperate in a concerted way to enable the chemical transformation. Experimental results on UiO-66 materials of different defectivity support the theoretical observations made in this work.
Keywords
DFT, kinetics, lewis acid site, bronsted base site, catalysis, METAL-ORGANIC FRAMEWORKS, INITIO MOLECULAR-DYNAMICS, TOTAL-ENERGY CALCULATIONS, WAVE BASIS-SET, LINKER DEFECTS, ADSORPTION, STABILITY, INSIGHT, OXIDES

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Chicago
Hajek, Julianna, Bart Bueken, Michel Waroquier, Dirk De Vos, and Veronique Van Speybroeck. 2017. “The Remarkable Amphoteric Nature of Defective UiO-66 in Catalytic Reactions.” Chemcatchem 9 (12): 2203–2210.
APA
Hajek, J., Bueken, B., Waroquier, M., De Vos, D., & Van Speybroeck, V. (2017). The remarkable amphoteric nature of defective UiO-66 in catalytic reactions. CHEMCATCHEM, 9(12), 2203–2210. Presented at the 1st French conference on Catalysis (FCCat).
Vancouver
1.
Hajek J, Bueken B, Waroquier M, De Vos D, Van Speybroeck V. The remarkable amphoteric nature of defective UiO-66 in catalytic reactions. CHEMCATCHEM. 2017;9(12):2203–10.
MLA
Hajek, Julianna, Bart Bueken, Michel Waroquier, et al. “The Remarkable Amphoteric Nature of Defective UiO-66 in Catalytic Reactions.” CHEMCATCHEM 9.12 (2017): 2203–2210. Print.
@article{8531598,
  abstract     = {One of the major requirements in solid acid and base catalyzed reactions is that the reactants, intermediates or activated complexes cooperate with several functions of catalyst support. In this work the remarkable bifunctional behavior of the defective UiO-66(Zr) metal organic framework is shown for acid-base pair catalysis. The active site relies on the presence of coordinatively unsaturated zirconium sites, which may be tuned by removing framework linkers and by removal of water from the inorganic bricks using a dehydration treatment. To elucidate the amphoteric nature of defective UiO-66, the Oppenauer oxidation of primary alcohols has been theoretically investigated using density functional theory (DFT) and the periodic approach. The presence of acid and basic centers within molecular distances is shown to be crucial for determining the catalytic activity of the material. Hydrated and dehydrated bricks have a distinct influence on the acidity and basicity of the active sites. In any case both functions need to cooperate in a concerted way to enable the chemical transformation. Experimental results on UiO-66 materials of different defectivity support the theoretical observations made in this work.},
  author       = {Hajek, Julianna and Bueken, Bart and Waroquier, Michel and De Vos, Dirk and Van Speybroeck, Veronique},
  issn         = {1867-3880},
  journal      = {CHEMCATCHEM},
  keyword      = {DFT,kinetics,lewis acid site,bronsted base site,catalysis,METAL-ORGANIC FRAMEWORKS,INITIO MOLECULAR-DYNAMICS,TOTAL-ENERGY CALCULATIONS,WAVE BASIS-SET,LINKER DEFECTS,ADSORPTION,STABILITY,INSIGHT,OXIDES},
  language     = {eng},
  location     = {Frejus, France},
  number       = {12},
  pages        = {2203--2210},
  title        = {The remarkable amphoteric nature of defective UiO-66 in catalytic reactions},
  url          = {http://dx.doi.org/10.1002/cctc.201601689},
  volume       = {9},
  year         = {2017},
}

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