Polyoxometalates confined in the mesoporous cages of metal–organic framework MIL-100(Fe): Efficient heterogeneous catalysts for esterification and acetalization reactions

Zhang, Fu‐Min; Jin, Yan; Shi, Jiyong; Zhong, Yijun; Zhu, Weidong; El‐Shall, M. Samy

doi:10.1016/j.cej.2015.01.092

Cited by 136 publications

(60 citation statements)

References 83 publications

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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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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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“…In the MIL‐100 MOF structure, the strong interaction between carboxylate groups of the small ligands and high‐valent metal ions (M 3+ ) preserve their frameworks with a superior physical and chemical stability, making them the ideal candidates being selected as an efficient catalyst . In this regard, [H 3 PW 12 O 40 ] (HPW 12 ) was encapsulated into a mesoporous MIL‐100(Fe) by Zhang's group . The prepared HPW 12 @MIL‐100(Fe) demonstrated a significant prospect for being employed as highly efficient in the liquid phase esterification of acetic acid with monohydric alcohols and acetalization reactions as solid acid catalysts.…”

Section: Applications Of Inorganic‐organic Hybrid Materials‐based On mentioning

confidence: 99%

“…The preparation and structural representation of HPW@MIL–100(Fe) hybrid. Figure reproduced from Ref., with permission of the copyright holders…”

Section: Applications Of Inorganic‐organic Hybrid Materials‐based On mentioning

confidence: 99%

Applications of inorganic‐organic hybrid architectures based on polyoxometalates in catalyzed and photocatalyzed chemical transformations

Lotfian

Heravi

Mirzaei

et al. 2019

Applied Organom Chemis

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The scope of this article is to reveal the fruitful combination of POM species with metal coordination complexes, leading to the construction of several efficient multifunctional catalysts. In this review, we try to underscore various catalytic and photocatalytic reactions catalyzed by POM‐based inorganic‐organic hybrid. Notably, it has been well established that depending on the type of the reaction, the activity and selectivity of these hybrid catalyst can be drastically improved by the rational and correct choice of the organic metal complex and POM anion providing a marriage of convenience.

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“…Microporous and mesoporous MOFs in comparison to zeolites give better molecular accessibility when it comes to larger substrates and products through bigger windows and pores. Among the MOFs, MIL‐101 shows good resistance to common solvents, water and temperature . Due to the high stability of MIL‐101 towards the leaching of Cr(ΙΙΙ) to solution, non‐carcinogenic and non‐mutagenic Cr(ΙΙΙ) compounds, it is an attractive compound as a support in heterogeneous catalysis .…”

Section: Introductionmentioning

confidence: 99%

In situ synthesis of metallophthalocyanines into pores of MIL‐101: A novel and green strategy for preparation of host–guest catalysts

Boroujeni

Hashemzadeh

Shaabani

et al. 2017

Applied Organom Chemis

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A novel strategy is developed to encapsulate metallophthalocyanines (MPcs, M = Cu, Ni and Co) into MIL-101 to give MPcs@MIL-101 via in situ synthesis of MPcs from component fragments in 1-butyl-3-methylimidazolium bromide as an ionic liquid. This strategy overcomes some drawbacks of existing methods for encapsulation of MPcs into metal-organic frameworks. The chemical and structural properties of MPcs@MIL-101 were determined using scanning electron microscopy, powder X-ray diffraction, and Fourier transformation infrared and flame atomic absorption spectroscopies. The results showed that CuPc@MIL-101, which was used as a 'ship-in-a-bottle' catalyst, demonstrates excellent catalytic performance in the oxidative amidation of aldehydes with amine salts. It is confirmed that CuPc@MIL-101 can be reused up to five times without significant loss of its activity.

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Polyoxometalates confined in the mesoporous cages of metal–organic framework MIL-100(Fe): Efficient heterogeneous catalysts for esterification and acetalization reactions

Cited by 136 publications

References 83 publications

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

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

Applications of inorganic‐organic hybrid architectures based on polyoxometalates in catalyzed and photocatalyzed chemical transformations

In situ synthesis of metallophthalocyanines into pores of MIL‐101: A novel and green strategy for preparation of host–guest catalysts

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