MOFs as multifunctional catalysts: one-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst

A bifunctional MOF catalyst containing coordinatively unsaturated Cr(3+) sites and palladium nanoparticles (Pd@MIL-101) has been used for the cyclization of citronellal to isopulegol and for the one-pot tandem isomerization/hydrogenation of citronellal to menthol. The MOF was found to be stable under the reaction conditions used, and the results obtained indicate that the performance of this bifunctional solid catalyst is comparable with other state-of-the-art materials for the tandem reaction: Full citronellal conversion was attained over Pd@MIL-101 in 18 h, with 86% selectivity to menthols and a diastereoselectivity of 81% to the desired (-)-menthol, while up to 30 h were necessary for attaining similar values over Ir/H-beta under analogous reaction conditions.     

ZnO-beta zeolite: as an effective and reusable heterogeneous catalyst for the one-pot synthesis of polyhydroquinolines

Abstract

ZnO-beta zeolite, an inexpensive and mild catalyst, has been used for the synthesis of polyhydroquinolines in excellent yields from the one-pot four-component condensation of aldehydes, dimedone, ethyl acetoacetate, and ammonium acetate in ethanol at room temperature. The remarkable advantages offered by this method are a green catalyst, mild reaction conditions, simple work-up procedures, much faster reactions, and excellent yield of products. Furthermore, the catalyst could be reused several times keeping its initial activity in recycled reactions.     

TS-1 zeolite as a Lewis acid catalyst for solvent-free one-pot synthesis of 1,3-thiazolidin-4-ones

Research on Chemical Intermediates - Titanium silicate (TS-1) zeolite heterogeneous catalyst is synthesized by the hydrothermally discontinuous method and is characterized by using XRD, SEM, TEM,...     

A general synthetic method for the formation of arylaminotetrazoles using natural natrolite zeolite as a new and reusable heterogeneous catalyst

An efficient method for preparation of arylaminotetrazoles is reported using natrolite zeolite as a natural catalyst. Generally, isomer of 5-arylamino-1H-tetrazole can be obtained from arylcyanamides carrying electron-withdrawing substituent on aryl ring and as the electropositivity of substituent is increased, the product is shifted toward the isomer of 1-aryl-5-amino-1H-tetrazole. This method has the advantages of high yields, simple methodology, short reaction times and easy work-up. The catalyst can be recovered by simple filtration and reused in good yields.     

Sn-Beta zeolite as diastereoselective water-resistant heterogeneous Lewis-acid catalyst for carbon-carbon bond formation in the intramolecular carbonyl-ene reaction

The water-tolerant Lewis acid Sn-Beta isomerises citronellal to isopulegol with high diastereoselectivity working in batch or in fixed bed reactors with very high turnover numbers.     

Template method for the synthesis of a heterogeneous fenton catalyst based on the hierarchical zeolite FeZSM-5

Zeolite h-FeZSM-5 with a hierarchical micro/macropore system has been synthesized in the presence of a template based on the close-packed polystyrene (PS) spheres, and the conventional zeolite FeZSM-5 has been obtained in the absence of a PS template. The zeolites have been characterized by X-ray diffraction, scanning and high-resolution transmission electron microscopy, and N₂ sorption. The macropore walls of the hierarchical zeolite consist of ZSM-5 nanocrystals and amorphous globules of silica. Compared to the conventional zeolite, the hierarchical one has a high BET and external surface areas of 245 and 472 m²/g, respectively, and a high pore volume of 0.6 cm³/g. The catalytic properties of the Fe-containing zeolites were studied in the H₂O₂ decomposition reaction in the absence and in the presence of EDTA ligands and in the oxidation of low- and high-molecular-weight organic compounds by hydrogen peroxide at 25°C. Hierarchical zeolite h-FeZSM-5 is highly efficient in the oxidation of large molecules.     

Hollow zeolite microspheres as a nest for enzymes: a new route to hybrid heterogeneous catalysts

In the field of heterogeneous catalysis, the successful integration of enzymes and inorganic catalysts could pave the way to multifunctional materials which are able to perform advanced cascade reactions. However, such combination is not straightforward, for example in the case of zeolite catalysts for which enzyme immobilization is restricted to the external surface. Herein, this challenge is overcome by developing a new kind of hybrid catalyst based on hollow zeolite microspheres obtained by the aerosol-assisted assembly of zeolite nanocrystals. The latter spheres possess open entry-ways for enzymes, which are then loaded and cross-linked to form cross-linked enzyme aggregates (CLEAs), securing their entrapment. This controlled design allows the combination of all the decisive features of the zeolite with a high enzyme loading. A chemo-enzymatic reaction is demonstrated, where the structured zeolite material is used both as a nest for the enzyme and as an efficient inorganic catalyst. Glucose oxidase (GOx) ensures the in situ production of H₂O₂ subsequently utilized by the TS-1 zeolite to catalyze the epoxidation of allylic alcohol toward glycidol. The strategy can also be used to entrap other enzymes or combination of enzymes, as demonstrated here with combi-CLEAs of horseradish peroxidase (HRP) and glucose oxidase. We anticipate that this strategy will open up new perspectives, leveraging on the spray-drying (aerosol) technique to shape microparticles from various nano-building blocks and on the entrapment of biological macromolecules to obtain new multifunctional hybrid microstructures.

A spray drying technique is used to prepare hollow zeolite microparticles into which an enzyme can be entrapped. Via this “Lego-like” strategy, we create hybrid heterogeneous catalysts that can run multistep chemo-enzymatic cascade reactions.     

Hydroxylated surface of GaAs as a scaffold for a heterogeneous Pd catalyst

A novel use of GaAs, namely, as a scaffold for a heterogeneous palladium catalyst, is proposed. Hydroxy groups on the GaAs surface play important roles. During the adsorption of Pd(OAc)(2) on the GaAs surface, the hydroxy groups attract Pd(ii) species by anion exchange. A subsequent redox reaction proceeds to generate Pd(0) nanoparticles, which are stabilized on the GaAs surface. This process is confirmed by surface-sensitive measurements: diffuse reflection IR spectroscopy and X-ray photoelectron spectroscopy. Moreover, a more bulk-sensitive measurement, hard X-ray photoemission spectroscopy with synchrotron radiation, also supported our considerations. The amounts of Pd(0) nanoparticles on the surface were evaluated by catalytic activity, yield, and recyclability in the Heck reaction, in addition to the deposit test.     

AgY zeolite as catalyst for the effective three-component synthesis of propargylamines

The preparation of substituted propargylamines via three-component reaction between aldehydes, terminal alkynes, and secondary amines following an environmentally acceptable methodology has been developed. The process has been carried out under solvent-free conditions in the presence of AgY zeolite. The catalyst can be easily recovered and reused for at least four cycles without significant decreases in yield and selectivity.     

Reduced graphene oxide-immobilized iron nanoparticles Fe(0)@rGO as heterogeneous catalyst for one-pot synthesis of series of propargylamines

Research on Chemical Intermediates - Iron nanoparticles immobilized on reduced graphene oxide (rGO), nanocomposite Fe(0)@rGO 1, were prepared in situ by reduction of GO and FeCl3·6H2O using...     

Polymer-supported zinc chloride: a highly active and reusable heterogeneous catalyst for one-pot synthesis of 2,4,5-trisubstituted imidazoles

Abstract  A polymer-supported Lewis acid catalyst was prepared and found to be extremely efficient for the preparation of imidazole derivatives via three-component condensation of benzil, aldehydes, and ammonium acetate under mild conditions. The catalyst is stable and can be easily recovered and reused at least four times without any loss of activity. Graphical Abstract        

A novel montmorillonite-enwrapped scandium as a heterogeneous catalyst for Michael reaction

Treatment of a Na+-exchanged montmorillonite with an aqueous Sc(OTf)3 solution afforded a robust Sc3+ aqua complex enwrapped by the silicate layers of the montmorillonites (Sc3+-mont). The resulting Sc3+-mont showed outstanding catalytic activities for the Michael reaction of 1,3-dicarbonyls under aqueous and solvent-free conditions. Moreover, this heterogeneous catalyst had an advantage of a strikingly simple workup procedure over the Lewis acids reported to date and was reusable without any appreciable losses in its activity and selectivity.     

ZnO-beta zeolite: As an effective and eco-friendly heterogeneous catalyst for the synthesis of benzothiazole derivatives

<正>A cheap and recyclable ZnO-beta zeolite was used as catalyst for the synthesis of benzothiazole derivatives.This method provides several advantages such as environmental friendliness,short reaction times,high yields,simple work-up procedure and catalyst was successfully reused for four cycles without significant loss of activity.     

Microparticle HZSM-5 zeolite as highly active catalyst for the hydration of cyclohexene to cyclohexanol

Microparticle HZSM-5 zeolite (MPZ) has been prepared without employing any organic templates, and used as a catalyst for the hydration of cyclohexene to synthesize cyclohexanol. MPZ exhibits better catalytic performance and superior settlement separation property than those of commercial HZSM-5 prepared by the traditional method using an organic template. The stability of MPZ has been investigated for a 1200-h test, and the regenerated performance of MPZ has also been investigated. The results show that although MPZ was reused for five recycles, the high cyclohexene conversion of 9.6 % and the high cyclohexanol selectivity of 96.8 % are still attained after the fifth regeneration. FT-IR, XRD and N₂ adsorption–desorption characterizations show that coke deposit on the surface and in the channels of MPZ is the main reason for the deactivation. ICP-AES, SEM–EDS and NH₃-TPD characterizations indicate that hydrothermal dealumination reduces the strong acidity and accelerates the catalyst deactivation. The spent catalyst by regeneration with H₂O₂ could be recovered to its initial high catalytic activity, due to the restored appropriate channels and exposed active sites.

     

Silica sulfuric acid (SSA) as a solid acid heterogeneous catalyst for one-pot synthesis of substituted pyrroles under solvent-free conditions at room temperature

A variety of N-substituted pyrroles have been synthesized by reacting γ-diketones with amines, diamines or triamine in the presence of silica sulfuric acid (SSA) at room temperature under solvent-free conditions. The experiment protocol features simple operations, and the products are isolated in high to excellent yields (70-98%).     

含NiY分子筛的加氢裂化催化剂载体研究

采用水热晶化法,合成出了含骨架杂原子Ni的NiY分子筛。分别以Y分子筛和NiY分子筛作为载体,通过等体积浸渍法担载金属活性组分Ni、Mo,制备加氢裂化催化剂。通过NH₃-TPD表征催化剂的表面酸性、固定床反应器评价催化剂的加氢裂化性能。结果表明,将Ni引入分子筛骨架中,可以调变催化剂的表面酸性,提高其裂化和脱硫活性,并减少催化剂上的积炭。