Sulfonyl chlorides as an efficient tool for the postsynthetic modification of Cr-MIL-101-SO<sub>3</sub>H and CAU-1-NH<sub>2</sub>

Klinkebiel, Arne; Reimer, Nele; Lammert, Martin; Stock, Norbert; Lüning, Ulrich

doi:10.1039/c4cc03746d

Cited by 21 publications

(11 citation statements)

References 37 publications

(8 reference statements)

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“…[50] MIL-101(Cr) and its aminoterephthalate-derivative NH 2 -MIL-101 (Cr) were already shown to be widely modifiable by postsynthetic modification (PSM). [51][52][53][54] The PSM approach of converting the amino functionality within NH 2 -MIL-101(Cr) into a urea-group by applying isocyanates has also already been exploited thoroughly. [55][56][57][58][59][60][61][62][63] In order to tailor the adsorption properties of MIL-101(Cr) compounds for SO 2 we synthesized and investigated four novel ureafunctionalized MOFs, namely URx-MIL-101(Cr) (x = 1, 2, 3 and 4, Figure 1).…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, the adsorption capacity of MIL‐101(Cr) for SO 2 changed very little in the concentration range from 0 to 2000 ppm SO 2 , when CO 2 was added to the adsorptive [50] . MIL‐101(Cr) and its aminoterephthalate‐derivative NH 2 ‐MIL‐101(Cr) were already shown to be widely modifiable by post‐synthetic modification (PSM) [51–54] …”

Section: Introductionmentioning

confidence: 99%

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A Series of new Urea‐MOFs Obtained via Post‐synthetic Modification of NH₂‐MIL‐101(Cr): SO₂, CO₂ and H₂O Sorption

Tannert

Sun

Hastürk

et al. 2021

Zeitschrift anorg allge chemie

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The amino group in the MOF NH 2 -MIL-101(Cr) was postsynthetically converted into urea-groups partially using either ethyl isocyanatoacetate, furfuryl isocyanate, p-toluenesulfonyl isocyanate or 3-(triethoxysilyl)propyl isocyanate in acetonitrile. The derived four novel urea-MOFs exhibit the expected lower BET surface areas and pore volumes than MIL-101(Cr) and NH 2 -MIL-101(Cr) MOFs but the partially p-toluenesulfonyl-ureamodified MOF exhibits an outstanding SO 2 adsorption capacity of 823 cm 3 g À 1 (corresponding to 36.7 mmol g À 1 or 70 wt.% at T = 0°C and 0.9 bar), which is the second highest SO 2 uptake of any known material today -surprisingly even better than for highly porous MIL-101(Cr) with an uptake of 645 cm 3 g À 1 SO 2 under the same conditions. The high uptake is linked to the favorable dipole interactions of SO 2 with the sulfonyl group of the p-toluenesulfonyl-modified MOF.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Series of new Urea‐MOFs Obtained via Post‐synthetic Modification of NH₂‐MIL‐101(Cr): SO₂, CO₂ and H₂O Sorption

Tannert

Sun

Hastürk

et al. 2021

Zeitschrift anorg allge chemie

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“…Among the well-studied MOFs, the chromium-based MIL-101 possesses several unique features such as a crystal structure consisting of two quasi-spherical mesoporous cages (2.9 and 3.4 nm, respectively), extremely large surface area, numerous unsaturated metal cation sites, and high stability in water [33]. The combination of these features makes MIL-101 a unique candidate for gas storage, drug delivery, adsorptive separation, and heterogeneous catalysis [34][35][36][37][38][39][40][41][42][43][44][45].…”

Section: Introductionmentioning

confidence: 99%

Palladium nanoparticles incorporated within sulfonic acid-functionalized MIL-101(Cr) for efficient catalytic conversion of vanillin

et al. 2015

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We report a highly efficient bifunctional catalyst, Pd/SO 3 H-MIL-101(Cr), consisting of Pd nanoparticles immobilized on a mesoporous sulfonic acid-functionalized metal-organic framework SO 3 H-MIL-101(Cr), which exhibits high catalytic performance in promoting biomass refining. The use of SO 3 H-MIL-101(Cr) as a support renders highly dispersed Pd nanoparticles with uniform size distribution, sufficient reactants contact in aqueous media, and rapid activation of the reactants induced by the Brønsted acid coordination sites (sulfonic acid groups from SO 3 H-MIL-101(Cr)). Thus, the 2.0 wt.% Pd/SO 3 H-MIL-101(Cr) catalyst exhibits novel synergy in the hydrodeoxygenation of vanillin (a typical model compound of lignin) at low H 2 pressure under mild conditions in aqueous media. Excellent catalytic results (100% conversion of vanillin with exclusive selectivity for the 2-methoxy-4-methylphenol product) could be achieved, and no loss of catalytic activity and selectivity were observed after seven recycles in succession.13 achieved over the 2.0 wt.% Pd/SO 3 H-MIL-101(Cr) catalyst including a 100% conversion of vanillin with a 100% selectivity for the 2-methoxy-4-methylphenol product within 120 min (entry 3 in Table 1). While in the presence of 2.0 wt.% Pd/MIL-101(Cr) catalyst, a rather low catalytic activity and selectivity were obtained when the reaction was carried out at the same conditions (entry 4). This is probably due to the lower acid strength of the MIL-101(Cr) as compared to that of the SO 3 H-MIL-101(Cr) support. Over the pure support SO 3 H-MIL-101(Cr) or MIL-101(Cr), however, no reaction took place, implying that Pd nanoparticles are inevitable for the vanillin hydrodeoxygenation (entries 1 and 2). Moreover, the 2.0 wt.% Pd/SO 3 H-MIL-101(Cr) catalyst was also compared with the commercially available Pd/C catalyst under the same conditions. The textural properties of the 2.0 wt.% Pd/C are shown in Table S1. The loading amounts of Pd within the Pd/SO 3 H-MIL-101(Cr), Pd/MIL-101(Cr) and Pd/C catalysts, determined by the ICP-AES analysis, were found to be 1.98 wt.%, 1.99 wt.% and 2.01 wt.%, respectively, very close to the nominal amount of 2.0 wt.%. The results (entry 5 in Table 1) clearly show that the 2.0 wt.% Pd/SO 3 H-MIL-101(Cr) catalyst gives significantly higher activity and 2-methoxy-4-methylphenol selectivity as compared to the Pd/C catalyst. It should be noted that the selectivity for 2-methoxy-4-methylphenol over the prepared 2.0 wt.% Pd/SO 3 H-MIL-101 catalyst is also significantly higher than that reported by Xiao et al [25] over 4.5 wt.% Pd/MSMF under the same reaction conditions with a similar conversion of vanillin (entry 6). The high selectivity over the 2.0 wt.% Pd/SO 3 H-MIL-101(Cr) catalyst is probably due to the readily accessible Brønsted acidic sites distributed throughout the framework as well as an abundance of mesoporous cages of MIL-101(Cr) thus, greatly facilitating the transfer of substrates [46,47].

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“…Two substituents R with considerably different electronic effects were selected: nitro (Hammett value: s m ¼ 0.71) and amino (Hammett value: s m ¼ À0. 16). While symmetrical 1,3,5-triazines can be synthesized by trimerization of nitriles [17e21], a modified synthetic route must be chosen for mono-substituted triazines [22,23].…”

Section: Resultsmentioning

confidence: 99%

Functionalized PCN-6 metal-organic frameworks

Mühlbauer

Klinkebiel

Beyer

et al. 2015

Microporous and Mesoporous Materials

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Sulfonyl chlorides as an efficient tool for the postsynthetic modification of Cr-MIL-101-SO₃H and CAU-1-NH₂

Cited by 21 publications

References 37 publications

A Series of new Urea‐MOFs Obtained via Post‐synthetic Modification of NH₂‐MIL‐101(Cr): SO₂, CO₂ and H₂O Sorption

A Series of new Urea‐MOFs Obtained via Post‐synthetic Modification of NH₂‐MIL‐101(Cr): SO₂, CO₂ and H₂O Sorption

Palladium nanoparticles incorporated within sulfonic acid-functionalized MIL-101(Cr) for efficient catalytic conversion of vanillin

Functionalized PCN-6 metal-organic frameworks

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Sulfonyl chlorides as an efficient tool for the postsynthetic modification of Cr-MIL-101-SO3H and CAU-1-NH2

Cited by 21 publications

References 37 publications

A Series of new Urea‐MOFs Obtained via Post‐synthetic Modification of NH2‐MIL‐101(Cr): SO2, CO2 and H2O Sorption

A Series of new Urea‐MOFs Obtained via Post‐synthetic Modification of NH2‐MIL‐101(Cr): SO2, CO2 and H2O Sorption

Palladium nanoparticles incorporated within sulfonic acid-functionalized MIL-101(Cr) for efficient catalytic conversion of vanillin

Functionalized PCN-6 metal-organic frameworks

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Product

Resources

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Sulfonyl chlorides as an efficient tool for the postsynthetic modification of Cr-MIL-101-SO₃H and CAU-1-NH₂

A Series of new Urea‐MOFs Obtained via Post‐synthetic Modification of NH₂‐MIL‐101(Cr): SO₂, CO₂ and H₂O Sorption

A Series of new Urea‐MOFs Obtained via Post‐synthetic Modification of NH₂‐MIL‐101(Cr): SO₂, CO₂ and H₂O Sorption