Immobilized VOsalpr on modified Fe3O4 nanoparticles as a magnetically separable epoxidation catalyst

Fe₃O₄ nanoparticles were prepared and modified with chloropropyl trimethoxysilane (Cl-PTMS). The N,N′-bis(3-salicylidenaminopropyl)amine (salpr) Schiff base ligand was then immobilized on modified Fe₃O₄, which was followed by the addition of VOSO₄ in order to complex it with immobilized sa0lpr. The obtained nanocatalyst designated as VO(Salpr)/SCMNPs was characterized by FT–IR, XRD, SEM, TEM, and VSM techniques. It was found that VO(salpr)/SCMNPs successfully catalyze the epoxidation of allyl alcohols, such as limonene, 1-octene-3-ol, trans-2-hexene-1-ol and geraniol with 50 to 100% conversion and 62 to 100% selectivity with tert-butylhydroperoxide (TBHP). The study of this catalyst's stability and reusability revealed that VO(salpr)/SCMNPs behaves heterogeneously with no desorption during the course of the epoxidation reactions.     

Facile synthesis of hierarchical core-shell Fe3O4@MgAl-LDH@Au as magnetically recyclable catalysts for catalytic oxidation of alcohols

A novel core-shell structural Fe(3)O(4)@MgAl-LDH@Au nanocatalyst was simply synthesized via supporting Au nanoparticles on the MgAl-LDH surface of Fe(3)O(4)@MgAl-LDH nanospheres. The catalyst exhibited excellent activity for the oxidation of 1-phenylethanol, and can be effectively recovered by using an external magnetic field.     

Fe3O4/MIL‐101(Fe) nanocomposite as an efficient and recyclable catalyst for Strecker reaction

A highly porous metal‐organic framework, MIL‐101(Fe), was prepared by a solvothermal method in the presence of amino‐modified Fe₃O₄@SiO₂ nanoparticles, in order to achieve Fe₃O₄/MIL‐101(Fe) nanocomposite, which was characterized by XRD, FT‐IR, SEM, TEM, BET, and VSM. This hybrid magnetic nanocomposite was employed as heterogeneous catalyst for α‐amino nitriles synthesis through three‐component condensation reaction of aldehydes (ketones), amines, and trimethylsilyl cyanide in EtOH, at room temperature. The recoverability and reusability was admitted for the heterogeneous magnetic catalyst; no significant reduction of catalytic activity was observed even after five consecutive reaction cycles.     

Fe3O4@dopa (dopa = dopamine hydrochloride) functionalized Mn(III) Schiff base complex: A promising magnetically separable heterogeneous catalyst for oxidative transformations

A chiral Schiff base complex has been prepared by treating (R)-1,2-diaminopropane with 3,5-dichlorosalicylaldehyde in ethanol, followed by addition of manganese chloride hexahydrate to generate a homogeneous catalyst, [MnL(Cl)(H₂O)] (HMN). Crystal structure of the complex reveals its mononuclear nature. Circular dichroism (CD) studies indicate that the ligand and its corresponding complex contain an asymmetric center. The catalytic activity of HMN toward epoxidation of alkenes, oxidation of alcohols and oxidation of alkanes has been investigated in the presence of iodosylbenzenediacetate (PhI(OAc)₂), in acetonitrile. In the present work we found yields to be much higher compared to our previous approaches. For further adaptation, we attached our efficient homogeneous catalyst with surface modified magnetic nanoparticles (Fe₃O₄@dopa) and thereby obtained a new magnetically separable nanocatalyst Fe₃O₄@dopa@MnLCl (FDM). This catalyst has been characterized and its oxidation ability assessed in similar conditions as those used for the homogeneous catalyst. Enantiomeric excess in epoxide yield reveals retention of chirality of the active site of Fe₃O₄@dopa@MnLCl. The catalyst can be recovered by magnetic separation and recycled several times without significant loss of catalytic activity.     

Oxoperoxo tungsten(VI) complex immobilized on Schiff base-modified Fe3O4 magnetic nanoparticles as a heterogeneous catalyst for oxidation of alcohols with hydrogen peroxide

Oxoperoxo tungsten(VI) complex immobilized on Schiff base-modified Fe₃O₄ super paramagnetic nanoparticles were synthesized and appropriately characterized using FT-IR, XRD, SEM, TEM, EDX, BET, and VSM analysis. The synthesized nanoparticles efficiently catalyzed oxidation of benzylic alcohols with H₂O₂ as oxidant in high yields, with high to excellent selectivity. The catalyst can be recovered using an external magnetic field and recycled for subsequent oxidation reactions without any appreciable loss of efficiency. The simple preparation, high activity, excellent selectivity, and simple recoverability of the catalyst are advantageous.     

Fe3O4-Lignin@Pd-NPs: A highly efficient,magnetically recoverable and recyclable catalyst for Mizoroki-Heck reaction under solvent-free conditions

Palladium nanoparticles ( Pd-NPs ) were synthesized under green conditions in water by chemical reduction of PdCl₂ with NaOH and supported by Fe ₃ O ₄ -Lignin . Fe ₃ O ₄ -Lignin is an organic–inorganic hybrid core-shell was synthesized by sonication of a mixture of Fe ₃ O ₄ -NPs (20 nm) and alkali lignin. The new materials Fe ₃ O ₄ -Lignin and Fe ₃ O ₄ -Lignin@Pd-NPs were characterized by PXRD, SEM and FT-IR spectroscopy. The Fe ₃ O ₄ -Lignin@Pd-NPs was further confirmed by UV–Visible spectroscopy, TEM, EDX, HRICP-AES and TGA/DTA. The average size of Pd-NPs determined from PXRD was 5–10 nm. The amount of palladium loaded on Fe ₃ O ₄ -Lignin obtained from EDX analysis was 26.63% by mass. The amount of Fe and Pd present in the catalyst obtained from HRICP-AES was 11.88 (wt. %) and 10.90 (wt. %) respectively per gram of lignin. The catalytic potential of Fe ₃ O ₄ -Lignin@Pd-NPs was evaluated in Mizoroki-Heck C-C coupling reaction. During the optimization studies of reaction between iodobenzene and n-butyl acrylate in various solvents and under solvent-free but aerobic conditions using various inorganic and organic bases, the product n-butyl 3-phenylprop-2-enoate ( 1a ) obtained was as high as 95% in highly polar solvents as short as in 10 min and 99% under solvent-free conditions in 3 min at 140 °C using n-Pr₃N as base. The scope of the above catalyst was investigated in the Mizoroki-Heck reaction of various aryl/heterocyclic halides and n-butyl acrylate/styrene under optimized solvent-less conditions. The corresponding products were obtained in high yields (73–99%). The catalyst recovered by magnetic decantation was reused for five times in the C-C coupling reaction between iodobenzene and n-butyl acrylate which yielded 90–95% of the desired product, 1a .     

Mn(III) complex supported on Fe3O4 nanoparticles: magnetically separable nanocatalyst for selective oxidation of thiols to disulfides

A manganese(III) complex, [Mn(phox)₂(CH₃OH)₂]ClO₄ (phox?=?2-(2′-hydroxyphenyl)oxazoline), was immobilized on silica-coated magnetic Fe₃O₄ nanoparticles through the amino propyl linkage using a grafting process in dichloromethane. The resulting Fe₃O₄@SiO₂–NH₂@Mn(III) nanoparticles are used as efficient and recyclable catalysts for selective oxidation of thiols to disulfides using urea-hydrogen peroxide as the oxidant. The nanocatalyst was recycled several times. Leaching and recycling experiments revealed that the nanocatalyst can be recovered, recycled, and reused more than five times, without the loss of catalytic activity and magnetic properties. The recycling of the nanocatalyst in six consecutive runs afforded a total turnover number of more than 10,000. The heterogeneous Fe₃O₄@SiO₂–NH₂@Mn(III) nanoparticle shows more selectivity for the formation of disulfides in comparison with the homogeneous manganese complex.     

Superparamagnetic Fe3O4 nanoparticles-carbon nitride nanotube hybrids for highly efficient peroxidase mimetic catalysts

We report a facile route to synthesize size tunable Fe(3)O(4) nanoparticles (NPs)-carbon nitride nanotube (CNNT) hybrids. These hybrids showing the water-soluble property are proven to exhibit ultra high peroxidase mimetic activity compared to those of pure NPs, where a colorless peroxidase substrate 3,3,5,5-tetramethylbenzidine changes by H(2)O(2) to its blue colored oxidized state.     

Ni@Pd core–shell nanoparticles immobilized on yolk–shell Fe3O4@polyaniline composites as a highly efficient,magnetically separable and atom‐economical catalyst for reduction of nitrobenzenes

The preparation of Ni@Pd core–shell nanoparticles immobilized on yolk–shell Fe₃O₄@polyaniline composites is reported. Fe₃O₄ nanoclusters were first synthesized through the solvothermal method and then the SiO₂ shell was coated on the Fe₃O₄ surface via a sol–gel process. To prepare Fe₃O₄@SiO₂@polyaniline composites, polyvinylpyrrolidone was first grafted on to the surface of Fe₃O₄@SiO₂ composites and subsequently polymerization of aniline was carried out via an ultrasound‐assisted in situ surface polymerization method. Selective etching of the middle SiO₂ layer was then accomplished to obtain the yolk–shell Fe₃O₄@polyaniline composites. The approach uses polyaniline (PANI) conductive polymer as a template for the synthesis of Ni@Pd core–shell nanoparticles. The catalytic activity of the synthesized yolk–shell Fe₃O₄@PANI/Ni@Pd composite was investigated in the reduction of o‐nitroaniline to benzenediamine by NaBH₄, which exhibited conversion of 99% in 3 min with a very low content of the catalyst. Transmission electron microscopy, X‐ray photoelectron spectroscopy, TGA, X‐ray diffraction, UV–visible, scanning electron microscopy, X‐ray energy dispersion spectroscopy and FT‐IR were employed to characterize the synthesized nanocatalyst. Copyright © 2014 John Wiley & Sons, Ltd.     

A cellulose-supported Mn(salen)Cl complex as an efficient heterogeneous catalyst for the selective oxidation of benzylic alcohols

[Mn(salen)Cl-cellulose] was synthesized by immobilization of homogeneous Mn(salen)Cl complex on cellulose and characterized by FT-IR, TGA and atomic absorption spectroscopy. The resulted catalyst exhibited moderate to high reactivity in the oxidation of benzylic alcohols into carbonyl compounds using oxone as oxidant in ambient conditions. The catalytic activity of Mn(salen)Cl and [Mn(salen)Cl-cellulose] in this reaction was investigated. The heterogeneous catalyst showed higher catalytic activity with respect to neat Mn(salen)Cl complex.     

Cu(II) Schiff base complex supported on Fe3O4 nanoparticles as an efficient nanocatalyst for the selective aerobic oxidation of alcohols

Herein, we have prepared a new Cu(II) Schiff base complex supported onto the surface of modified Fe₃O₄ nanoparticles as highly stable, heterogeneous and magnetically recyclable nanocatalyst for the selective aerobic oxidation of different alcohols. The structure, morphology, chemical composition and magnetic property of the nanocatalyst and its precursors were characterized using FT‐IR, TGA, AAS, ICP‐AES, XRD, SEM, EDS, VSM and N₂ adsorption–desorption analyses. Characterization results exhibited the uniform spherical morphology for nanocatalyst and its precursors. A promising eco‐friendly method with short reaction time and high conversion and selectivity for oxidation of various primary and secondary alcohols under O₂ atmosphere condition was achieved. The synthesized nanocatalyst could be recovered easily by applying an external magnetic field and reused for least eight subsequent reaction cycles with only negligible deterioration in catalytic performance.     

Synthesis and characterization of bromine source supported on magnetic Fe3O4 nanoparticles: A new,versatile and efficient magnetically separable catalyst for organic synthesis

Tribenzylammonium tribromide supported onto magnetic nanoparticles (Br₃‐TBA‐Fe₃O₄) as a bromine source was successfully synthesized and characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and vibrating sample magnetometry. The synthesized catalyst is shown to be a versatile and highly efficient heterogeneous catalyst for the Knoevenagel condensation and synthesis of 2,3‐dihydroquinazolin‐4(1H )‐one and polyhydroquinoline derivatives. To the best of the authors' knowledge, this is the first report of the use of a bromine source immobilized on Fe₃O₄ nanoparticles as a magnetically separable catalyst for these reactions. The nanosolid catalyst can be magnetically recovered and reused readily several times without significant loss in catalytic efficiency.     

Selectively deposited noble metal nanoparticles on Fe3O4/graphene composites: stable, recyclable, and magnetically separable catalysts

A simple, efficient, and general approach was developed to selectively deposit noble metal (Pt, Pd, or PtPd) nanoparticles 3-5?nm in size on magnetite/graphene composites. The biomolecule L-lysine with two kinds of functional groups (NH(2) and COOH) played the key role of connecter between noble metals and Fe(3)O(4)/graphene composites. These composites were characterized by TEM, XRD, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results indicated that the noble metals are mostly dispersed on the magnetite surfaces of the composites. The as-obtained composites are ideal recyclable catalysts for liquid-phase reactions owing to their stability and efficient magnetic separation. Among these catalysts, the PtPd-based composites exhibited the highest activity and resistance to poisoning during the catalytic reduction of 4-nitrophenol to 4-aminophenol by NaBH(4). Such hybrid catalysts obtained by this simple, efficient method are expected to find use in industrial applications, where separation and recycling are critically required to reduce cost and waste production.     

Palladium nanoparticles immobilized on EDTA‐modified Fe3O4@SiO2 nanospheres as an efficient and magnetically separable catalyst for Suzuki and Sonogashira cross‐coupling reactions

In this study, a novel heterogeneous palladium catalyst was synthesized by anchoring palladium onto ethylenediaminetetraacetic acid (EDTA)‐coated Fe₃O₄@SiO₂ magnetic nanocomposite and used for the Suzuki and Sonogashira cross‐coupling reactions. The properties of the magnetic catalyst were characterized by FT‐IR, XRD, TEM, FE‐SEM, DLS EDX, XPS, N₂ adsorption‐desorption isotherm analysis, TGA, VSM, elemental analysis and the loading level of Pd in catalyst was measured to be 0.51 mmol/g by ICP. The catalyst was used in Suzuki cross‐coupling reactions of various aryl halides, including less reactive chlorobenzenes with phenylboronic acid without any additive or ligand under green conditions. Furthermore, we have reported this recyclable catalytic system for Sonogashira cross‐coupling reactions of various aryl halides (I, Br, Cl) under copper and ligand‐free conditions in the presence of DMF/H₂O (1:2/v:v) as a solvent. The magnetic catalyst could also be separated by an external magnet and reused six times without any significant loss of activity.     

A novel magnetically separable laccase-mediator catalyst system for the aerobic oxidation of alcohols and 2-substituted-2,3-dihydroquinazolin-4(1H)-ones under mild conditions

In this study, a magnetically reusable artificial metalloenzyme has been constructed by co-immobilization of palladium nanoparticles as a strong oxidizing catalyst and laccase as an oxygen-activating enzyme into the cavities of magnetic mesocellular foams silica (Pd-Laccase@MMCF). The combination of Pd-Laccase@MMCF and hydroquinone (HQ) act as electron-transfer mediator system and make stepwise electron transfer from substrate to molecular oxygen. This catalyst system was used for the aerobic (i) oxidation of alcohols to the corresponding carbonyl compounds and (ii) dehydrogenation of 2-substituted-2,3-dihydroquinazolin-4(1H)-ones in phosphate buffer (0.1 M, pH 4.5, 4 mL)/THF (4%, 1 mL) as solvent under mild conditions. The co-immobilization of both laccase and Pd onto high surface area mesoporous support, high catalytic activity and magnetically separable and reusable make the present catalyst system superior to other currently available electron-transfer mediator systems.     

Tetrazole derivatives synthesis using Fe3O4@fibroin-SO3H as a magnetically separable green solid acid nanocatalyst under solvent-free conditions

Research on Chemical Intermediates - In the present study, a magnetically separable potent solid acid nanocatalyst with a facile preparation technique was fabricated via incorporation of fibroin as...     

Synthesis and characterization of sulfamic acid supported on Fe3O4 nanoparticles: A green,versatile and magnetically separable acidic catalyst for oxidation reactions and Knoevenagel condensation

Sulfamic acid immobilized on diethylenetriamine functionalized Fe₃O₄ nanoparticles (SA‐DETA‐Fe₃O₄) was successfully prepared and characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), vibrating sample magnetometer (VSM), thermo gravimetric analysis (TGA), X‐Ray diffraction (XRD) and scanning electron microscopy (SEM). The sulfamic acid was found as a magnetically separable and highly active catalyst for the oxidative coupling thiols, oxidation of sulfides. Furthermore, the SA‐DETA‐Fe₃O₄ showed the high catalytic activity in Knoevenagel condensation of aromatic aldehydes with active methylene compounds (malononitrile and ethyl cynoacetate). The nanosolid catalyst could be easily recovered by a simple magnetic separation and reused for many cycles without deterioration in catalytic activity.