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Influence of a confined methanol solvent on the reactivity of active sites in UiO-66

(2018) CHEMPHYSCHEM. 19(4). p.420-429
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Abstract
UiO-66, composed of Zr-oxide bricks and terephthalate linkers, is currently one of the most studied metal-organic frameworks due to its exceptional stability. Defects can be introduced in the structure, creating undercoordinated Zr atoms which are Lewis acid sites. Here, additional BrOnsted sites can be generated by coordinated protic species from the solvent. In this Article, a multilevel modeling approach was applied to unravel the effect of a confined methanol solvent on the active sites in UiO-66. First, active sites were explored with static periodic density functional theory calculations to investigate adsorption of water and methanol. Solvent was then introduced in the pores with grand canonical Monte Carlo simulations, followed by a series of molecular dynamics simulations at operating conditions. A hydrogen-bonded network of methanol molecules is formed, allowing the protons to shuttle between solvent methanol, adsorbed water, and the inorganic brick. Upon deprotonation of an active site, the methanol solvent aids the transfer of protons and stabilizes charged configurations via hydrogen bonding, which could be crucial in stabilizing reactive intermediates. The multilevel modeling approach adopted here sheds light on the important role of a confined solvent on the active sites in the UiO-66 material, introducing dynamic acidity in the system at finite temperatures by which protons may be easily shuttled from various positions at the active sites.
Keywords
ab initio calculations, hydrogen transfer, molecular dynamics, solvent effects, UiO-66, METAL-ORGANIC FRAMEWORKS, INITIO MOLECULAR-DYNAMICS, TOTAL-ENERGY CALCULATIONS, AUGMENTED-WAVE METHOD, DEFECTIVE UIO-66, LIQUID METHANOL, FORCE-FIELD, BASIS-SET, SIMULATIONS, WATER

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Chicago
Caratelli, Chiara, Julianna Hajek, Sven Rogge, Steven Vandenbrande, Evert Jan Meijer, Michel Waroquier, and Veronique Van Speybroeck. 2018. “Influence of a Confined Methanol Solvent on the Reactivity of Active Sites in UiO-66.” Chemphyschem 19 (4): 420–429.
APA
Caratelli, C., Hajek, J., Rogge, S., Vandenbrande, S., Meijer, E. J., Waroquier, M., & Van Speybroeck, V. (2018). Influence of a confined methanol solvent on the reactivity of active sites in UiO-66. CHEMPHYSCHEM, 19(4), 420–429.
Vancouver
1.
Caratelli C, Hajek J, Rogge S, Vandenbrande S, Meijer EJ, Waroquier M, et al. Influence of a confined methanol solvent on the reactivity of active sites in UiO-66. CHEMPHYSCHEM. 2018;19(4):420–9.
MLA
Caratelli, Chiara, Julianna Hajek, Sven Rogge, et al. “Influence of a Confined Methanol Solvent on the Reactivity of Active Sites in UiO-66.” CHEMPHYSCHEM 19.4 (2018): 420–429. Print.
@article{8562408,
  abstract     = {UiO-66, composed of Zr-oxide bricks and terephthalate linkers, is currently one of the most studied metal-organic frameworks due to its exceptional stability. Defects can be introduced in the structure, creating undercoordinated Zr atoms which are Lewis acid sites. Here, additional BrOnsted sites can be generated by coordinated protic species from the solvent. In this Article, a multilevel modeling approach was applied to unravel the effect of a confined methanol solvent on the active sites in UiO-66. First, active sites were explored with static periodic density functional theory calculations to investigate adsorption of water and methanol. Solvent was then introduced in the pores with grand canonical Monte Carlo simulations, followed by a series of molecular dynamics simulations at operating conditions. A hydrogen-bonded network of methanol molecules is formed, allowing the protons to shuttle between solvent methanol, adsorbed water, and the inorganic brick. Upon deprotonation of an active site, the methanol solvent aids the transfer of protons and stabilizes charged configurations via hydrogen bonding, which could be crucial in stabilizing reactive intermediates. The multilevel modeling approach adopted here sheds light on the important role of a confined solvent on the active sites in the UiO-66 material, introducing dynamic acidity in the system at finite temperatures by which protons may be easily shuttled from various positions at the active sites.},
  author       = {Caratelli, Chiara and Hajek, Julianna and Rogge, Sven and Vandenbrande, Steven and Meijer, Evert Jan and Waroquier, Michel and Van Speybroeck, Veronique},
  issn         = {1439-4235},
  journal      = {CHEMPHYSCHEM},
  keyword      = {ab initio calculations,hydrogen transfer,molecular dynamics,solvent effects,UiO-66,METAL-ORGANIC FRAMEWORKS,INITIO MOLECULAR-DYNAMICS,TOTAL-ENERGY CALCULATIONS,AUGMENTED-WAVE METHOD,DEFECTIVE UIO-66,LIQUID METHANOL,FORCE-FIELD,BASIS-SET,SIMULATIONS,WATER},
  language     = {eng},
  number       = {4},
  pages        = {420--429},
  title        = {Influence of a confined methanol solvent on the reactivity of active sites in UiO-66},
  url          = {http://dx.doi.org/10.1002/cphc.201701109},
  volume       = {19},
  year         = {2018},
}

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