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Engineering a highly defective stable UiO-66 with tunable Lewis-Brønsted acidity : the role of the hemilabile linker

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  • DYNPOR (First principle molecular dynamics simulations for complex chemical transformations in nanoporous materials)
Abstract
The stability of metal-organic frameworks (MOFs) typically decreases with an increasing number of defects, limiting the number of defects that can be created and limiting catalytic and other applications. Herein, we use a hemilabile (Hl) linker to create up to a maximum of six defects per cluster in UiO-66. We synthesized hemilabile UiO-66 (Hl-UiO-66) using benzene dicarboxylate (BDC) as linker and 4-sulfonatobenzoate (PSBA) as the hemilabile linker. The PSBA acts not only as a modulator to create defects but also as a coligand that enhances the stability of the resulting defective framework. Furthermore, upon a postsynthetic treatment in H2SO4, the average number of defects increases to the optimum of six missing BDC linkers per cluster (three per formula unit), leaving the Zr-nodes on average sixfold coordinated. Remarkably, the thermal stability of the materials further increases upon this treatment. Periodic density functional theory calculations confirm that the hemilabile ligands strengthen this highly defective structure by several stabilizing interactions. Finally, the catalytic activity of the obtained materials is evaluated in the acid-catalyzed isomerization of a-pinene oxide. This reaction is particularly sensitive to the Bronsted or Lewis acid sites in the catalyst. In comparison to the pristine UiO-66, which mainly possesses Bronsted acid sites, the Hl-UiO-66 and the postsynthetically treated Hl-UiO-66 structures exhibited a higher Lewis acidity and an enhanced activity and selectivity. This is further explored by CD3CN spectroscopic sorption experiments. We have shown that by tuning the number of defects in UiO-66 using PSBA as the hemilabile linker, one can achieve highly defective and stable MOFs and easily control the Bronsted to Lewis acid ratio in the materials and thus their catalytic activity and selectivity.
Keywords
Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis, METAL-ORGANIC FRAMEWORKS, INITIO MOLECULAR-DYNAMICS, TOTAL-ENERGY CALCULATIONS, ALPHA-PINENE OXIDE, CATALYTIC-ACTIVITY, PROTON TOPOLOGY, ACTIVE-SITES, ZR, ISOMERIZATION, SPECTROSCOPY

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Citation

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MLA
Feng, Xiao, et al. “Engineering a Highly Defective Stable UiO-66 with Tunable Lewis-Brønsted Acidity : The Role of the Hemilabile Linker.” JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 142, no. 6, 2020, pp. 3174–83.
APA
Feng, X., Hajek, J., Jena, H., Wang, G., Kaliya Perumal Veerapandian, S., Morent, R., … Van Der Voort, P. (2020). Engineering a highly defective stable UiO-66 with tunable Lewis-Brønsted acidity : the role of the hemilabile linker. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 142(6), 3174–3183.
Chicago author-date
Feng, Xiao, Julianna Hajek, Himanshu Jena, Guangbo Wang, Savita Kaliya Perumal Veerapandian, Rino Morent, Nathalie De Geyter, et al. 2020. “Engineering a Highly Defective Stable UiO-66 with Tunable Lewis-Brønsted Acidity : The Role of the Hemilabile Linker.” JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 142 (6): 3174–83.
Chicago author-date (all authors)
Feng, Xiao, Julianna Hajek, Himanshu Jena, Guangbo Wang, Savita Kaliya Perumal Veerapandian, Rino Morent, Nathalie De Geyter, Karen Leyssens, Alexander Hoffman, Vera Meynen, Carlos Marquez, Dirk E De Vos, Veronique Van Speybroeck, Karen Leus, and Pascal Van Der Voort. 2020. “Engineering a Highly Defective Stable UiO-66 with Tunable Lewis-Brønsted Acidity : The Role of the Hemilabile Linker.” JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 142 (6): 3174–3183.
Vancouver
1.
Feng X, Hajek J, Jena H, Wang G, Kaliya Perumal Veerapandian S, Morent R, et al. Engineering a highly defective stable UiO-66 with tunable Lewis-Brønsted acidity : the role of the hemilabile linker. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 2020;142(6):3174–83.
IEEE
[1]
X. Feng et al., “Engineering a highly defective stable UiO-66 with tunable Lewis-Brønsted acidity : the role of the hemilabile linker,” JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 142, no. 6, pp. 3174–3183, 2020.
@article{8644253,
  abstract     = {The stability of metal-organic frameworks (MOFs) typically decreases with an increasing number of defects, limiting the number of defects that can be created and limiting catalytic and other applications. Herein, we use a hemilabile (Hl) linker to create up to a maximum of six defects per cluster in UiO-66. We synthesized hemilabile UiO-66 (Hl-UiO-66) using benzene dicarboxylate (BDC) as linker and 4-sulfonatobenzoate (PSBA) as the hemilabile linker. The PSBA acts not only as a modulator to create defects but also as a coligand that enhances the stability of the resulting defective framework. Furthermore, upon a postsynthetic treatment in H2SO4, the average number of defects increases to the optimum of six missing BDC linkers per cluster (three per formula unit), leaving the Zr-nodes on average sixfold coordinated. Remarkably, the thermal stability of the materials further increases upon this treatment. Periodic density functional theory calculations confirm that the hemilabile ligands strengthen this highly defective structure by several stabilizing interactions. Finally, the catalytic activity of the obtained materials is evaluated in the acid-catalyzed isomerization of a-pinene oxide. This reaction is particularly sensitive to the Bronsted or Lewis acid sites in the catalyst. In comparison to the pristine UiO-66, which mainly possesses Bronsted acid sites, the Hl-UiO-66 and the postsynthetically treated Hl-UiO-66 structures exhibited a higher Lewis acidity and an enhanced activity and selectivity. This is further explored by CD3CN spectroscopic sorption experiments. We have shown that by tuning the number of defects in UiO-66 using PSBA as the hemilabile linker, one can achieve highly defective and stable MOFs and easily control the Bronsted to Lewis acid ratio in the materials and thus their catalytic activity and selectivity.},
  author       = {Feng, Xiao and Hajek, Julianna and Jena, Himanshu and Wang, Guangbo and Kaliya Perumal Veerapandian, Savita and Morent, Rino and De Geyter, Nathalie and Leyssens, Karen and Hoffman, Alexander and Meynen, Vera and Marquez, Carlos and De Vos, Dirk E and Van Speybroeck, Veronique and Leus, Karen and Van Der Voort, Pascal},
  issn         = {0002-7863},
  journal      = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY},
  keywords     = {Colloid and Surface Chemistry,Biochemistry,General Chemistry,Catalysis,METAL-ORGANIC FRAMEWORKS,INITIO MOLECULAR-DYNAMICS,TOTAL-ENERGY CALCULATIONS,ALPHA-PINENE OXIDE,CATALYTIC-ACTIVITY,PROTON TOPOLOGY,ACTIVE-SITES,ZR,ISOMERIZATION,SPECTROSCOPY},
  language     = {eng},
  number       = {6},
  pages        = {3174--3183},
  title        = {Engineering a highly defective stable UiO-66 with tunable Lewis-Brønsted acidity : the role of the hemilabile linker},
  url          = {http://dx.doi.org/10.1021/jacs.9b13070},
  volume       = {142},
  year         = {2020},
}

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