Core-shell zirconia-coated magnetic nanoparticles offering a strong option to prepare a novel and magnetized heteropolyacid based heterogeneous nanocatalyst for three- and four-component reactions

A new type of magnetically-separable nanocatalyst was prepared through the immobilization of phosphomolybdic acid (H₃PMo₁₂O₄₀) in 10–30 wt.% on the surface of core-shell zirconia-coated magnetite nanoparticle (nano-Fe₃O₄@ZrO₂). The developed heterogeneous nano-sized acid catalyst named nano-Fe₃O₄@ZrO₂ supported PMA (or n-Fe₃O₄@ZrO₂/PMA) was characterized using several techniques such as FT-IR, XRD, FE-SEM, VSM, EDX, TEM and TGA. The characterization data derived from FT-IR spectroscopy exhibited that H₃PMo₁₂O₄₀ species on the support retained their Keggin structures. Additionally, the potentiometric titration with n-butylamine was employed to measure the acidity content of the as-obtained catalyst. Surprisingly, this novel active solid acid catalyst displayed to have a higher number of surface active sites compared to its homogeneous analogues. Besides, the catalytic activity of the catalyst was evaluated in multicomponent reactions (MRCs) for the rapid and efficient one-pot synthesis of 2, 4, 5-trisubstituted and 1, 2, 4, 5-tetrasubstituted imidazoles in high yields and selectivity. The sample of 20 wt.% displayed higher acidity content which led to its enhanced activity in the catalytic transformation. Moreover, the catalyst could be easily reused without deactivation after five runs, which made it a promising catalyst for practical and large-scale applications. This outstanding reusability was ascribed to the strong attachment of PMA molecules on the n-Fe₃O₄@ZrO₂ support material.     

Magnetically recoverable AlFe/Te nanocomposite as a new catalyst for the facile esterification reaction under neat conditions

In this work, a new Fe₃O₄/AlFe/Te nanocomposite was synthesized by a one‐step sol–gel method. The Fe₃O₄ magnetic nanoparticles (MNPs) were prepared and then mixed with aluminum telluride (Al₂Te₃) in an alkali medium to produce the desired catalyst. After characterization of the Fe₃O₄/AlFe/Te nanocomposite by SEM, TEM, EDS, XRD, and ICP analyses, it was used in the esterification reaction. This heterogeneous catalyst showed high catalytic activity in the esterification of commercially available carboxylic acids with various alcohols to produce the desired esters at high conversions under neat conditions. The Fe₃O₄/AlFe/Te nanocomposites were separated from the reaction mixture via an external magnet and re‐used 8 times without significant loss of catalytic activity.     

Magnetic graphene nanocomposite as an efficient catalyst for hydrogenation of nitroarenes

Graphene-Fe₃O₄ nanocomposite（G-Fe₃O₄） was synthesized by a chemical co-precipitation method which was used as an efficient catalyst for the reduction of nitroarenes with hydrazine hydrate.The method has been applied to a broad range of compounds with different properties and the yields were in the range of 75%-92%.The G-Fe₃O₄ catalyst can be readily recovered and reused 5 times without significant loss of the catalytic activity.     

Magnetically separable g‐C3N4 hybrid nanocomposite: Highly efficient and eco‐friendly recyclable catalyst for one‐pot synthesis of α‐aminonitriles

A magnetically separable graphitic carbon nitride nanocomposite (Fe₃O₄/g‐C₃N₄) as a catalyst for the three‐component condensation reactions of carbonyl compounds, amines and trimethylsilylcyanide was thoroughly investigated. The reaction of these three components was found to be efficient, economical and green and took place in the presence of a catalytic amount of the magnetically separable catalyst to yield the corresponding α‐aminonitriles in good to excellent yields. The prepared nanocomposite was characterized using scanning electron microscopy and energy‐dispersive X‐ray and Fourier transform infrared spectroscopies. The nanocomposite was also found to be reusable could be recovered easily and reused several times without distinct deterioration in its catalytic activity.     

Ionic Liquid-Assisted Fabrication of Bioactive Heterogeneous Magnetic Nanocatalyst with Antioxidant and Antibacterial Activities for the Synthesis of Polyhydroquinoline Derivatives

Antibacterial materials have obtained much attention in recent years due to the presence of hazardous agents causing oxidative stress and observation of pathogens. However, materials with antioxidant and antibacterial activities can cause toxicity due to their low biocompatibility and safety profile, urging scientists to follow new ways in the synthesis of such materials. Ionic liquids have been employed as a green and environmentally solvent for the fabrication of electrically conductive polymers. In the present study, an antibacterial poly(p-phenylenediamine)@Fe₃O₄ (PpPDA@Fe₃O₄) nanocomposite was fabricated using [HPy][HSO₄] ionic liquid. The chemical preparation of PpPDA@Fe₃O₄ nanocomposite was initiated through the oxidative polymerization of p-phenylenediamine by ammonium persulfate in the presence of [HPy][HSO₄]. The PpPDA@Fe₃O₄ nanocomposite exhibited antibacterial properties against Gram-negative (Escherichia coli) and Gram-positive (Bacillus subtilis) bacteria. The PpPDA@Fe₃O₄ nanocomposite was employed as a heterogeneous nanocatalysis for one-pot synthesis of polyhydroquinoline derivatives using aromatic aldehyde, dimedone, benzyl acetoacetate, and ammonium acetate. Polyhydroquinoline derivatives were synthesized in significant yields (90–97%) without a difficult work-up procedure in short reaction times. Additionally, PpPDA@Fe₃O₄ nanocatalyst was recycled for at least five consecutive catalytic runs with a minor decrease in the catalytic activity. In this case, 11 derivatives of polyhydroquinoline showed in vitro antioxidant activity between 70–98%.     

Preparation of a trihydrazinotriazine-functionalized core-shell nanocatalyst as an extremely efficient catalyst for the synthesis of benzoxanthenes

In recent years, there is a high demand on utilizing heterogeneous nanocatalysts in organic synthetic routes because of their green approach, facile purification of the products, and reusability of the catalyst. Herein, we introduced trihydrazinotriazine (THDT)-coated Fe₃O₄@SiO₂ as a novel amino-functionalized magnetic nanocompostie. We fully characterized the nanocatalyst and proved the morphology and magnetic property of the nanoparticles by using essential analyses. The basic attribute of the amino-rich porous surface of the nanocomposite provides a desirable environment for enhancing various reaction conditions. To examine the applicability of the nanocatalyst in organic reactions, we synthesized several benzoxanthenes using Fe₃O₄@SiO₂-THDT nanocatalysts. The nanocomposite successfully improved the reaction conditions and provided the benzoxanthenes in an environmentally friendly procedure, which afforded product in excellent yields (80–96%) and reduced time. The nanomagnetic catalyst was easily recovered after each trial by using an external magnet. After six successive runs, the loss of catalytic activity of the nanocomposite was negligible. Finally, we propounded a plausible mechanism for the preparation of the benzoxanthenes derivatives using the THDT-functionalized core-shell magnetic nanocatalyst.     

3-Amino-5-mercapto-1,2,4-triazole-functionalized Fe3O4 magnetic nanocomposite as a green and efficient catalyst for synthesis of bis(indolyl)methane derivatives

A core–shell Fe₃O₄@silica magnetic nanocomposite functionalized with 3-amino-5-mercapto-1,2,4-triazole (Fe₃O₄/SiO₂/PTS/AMTA) was prepared using Fe₃O₄ with silica layer, and its surface was modified with 3-amino-5-mercapto-1,2,4-triazole. The novel synthesized magnetite nanocomposite was characterized using various techniques. The catalytic activity of Fe₃O₄/SiO₂/PTS/AMTA was demonstrated in the synthesis of bis(indolyl)methane derivatives under solvent-free conditions. Some of the bis(indolyl)methane derivatives were synthesized through one-pot, three-component reaction of 1 mol of various benzaldehydes or ketones with 2 mol of indole in the presence of Fe₃O₄/SiO₂/PTS/AMTA in good to excellent isolated yields. In addition, the catalyst could be recovered and used for several reaction runs without loss of catalytic activity. The stability of recycled catalyst was investigated. This method has some advantages including experimental simplicity, good to excellent yields, solvent-free conditions and stability and reusability of the catalyst.     

Fe3O4 MNPs-DETA/Benzyl-Br3: A new magnetically reusable catalyst for the oxidative coupling of thiols

We report a new strategy to immobilize a bromine source on the surface of magnetic Fe₃O₄ nanoparticles (Fe₃O₄ MNPs-DETA/Benzyl-Br₃) leading to a magnetically recoverable catalyst, which exhibits high catalytic efficiency in oxidative coupling of thiols to the disulfides (89–98%). The Fe₃O₄ MNPs-DETA/Benzyl-Br₃ catalyst was fabricated by anchoring 3-chloropropyltrimethoxysilane (CPTMS) on magnetic Fe₃O₄ nanoparticles, followed with N-benzylation and reaction with bromine in tetrachloridecarbon. The resulting nanocomposite was analyzed by a series of characterization techniques such as FT-IR, SEM, TGA, VSM and XRD. The catalyst could be recovered via magnetic attraction and could be recycled at least 5 times without appreciable decrease in activity.     

Synthesis of a highly active amino‐functionalized Fe3O4@SiO2/APTS/Ru magnetic nanocomposite catalyst for hydrogenation reactions

An amino‐functionalized silica‐coated Fe₃O₄ nanocomposite (Fe₃O₄@SiO₂/APTS) was synthesized. The Fe₃O₄@SiO₂ microspheres possessed a well‐defined core–shell structure, uniform sizes and high magnetization. An immobilized ruthenium nanoparticle catalyst (Fe₃O₄@SiO₂/APTS/Ru) was obtained after coordination and reduction of Ru³⁺ on the Fe₃O₄@SiO₂/APTS nanocomposite. The Ru nanoparticles were not only ultra‐small with nearly monodisperse sizes but also had strong affinity with the surface of Fe₃O₄@SiO₂/APTS. The obtained catalyst exhibited excellent catalytic performance for the hydrogenation of a variety of aromatic nitro compounds, even at room temperature. Moreover, Fe₃O₄@SiO₂/APTS/Ru was easily recovered using a magnetic field and directly reused for at least five cycles without significant loss of its activity.     

Fabrication of magnetically separable palladium–graphene nanocomposite with unique catalytic property of hydrogenation

One step solvothermal route has been developed to prepare a well dispersed magnetically separable palladium–graphene nanocomposite, which can act as a unique catalyst against hydrogenation due to the uniform decoration of palladium nanoparticles throughout the surface of the magnetite–graphene nanocomposite and hence can be reused for several times. In addition to catalytic activity, palladium nanoparticles also facilitate the formation and homogeneous distribution of magnetite (Fe₃O₄) nanoparticles onto the graphene surfaces or else an agglomerated product has been obtained after the solvothermal reduction of graphene oxide in presence of Fe³⁺ alone.     

Co3O4-decorated carbon nanotubes as a novel efficient catalyst in the selective oxidation of benzoins

An efficient and facile air oxidation of benzoins in the presence of the heterogeneous catalyst, Co₃O₄–CNTs nanocomposite, has been developed. It thus constitutes a very simple, clean, economical and selective method for the aerobic preparation of benzils from the corresponding benzoins. The catalyst can be re-used a number of times without losing its catalytic activity to a greater extent.     

Fe3O4-Graphene oxide nanocomposite: Synthesis of 5-sulfanyl tetrazole derivatives of alkyls,indoles, and pyrroles

In this work, the use of Fe₃O₄/geraphene oxide nanocomposite as an efficient catalyst for the synthesis of 5-sulfanyltetrazole derivatives of indoles, pyrroles, and 5-alkyl sulfanyltetrazoles is described. These compounds are readily obtained by the reaction of the starting heterocycles indoles, N-aryl pyrroles, alkyl thiocyanates, and trimethylsilyl azide in good to excellent yields. Moreover, Fe₃O₄/GO nanocomposite could be easily separated from the reaction mixtures by an external permanent magnet and reused at least six times continuously without significant reduction in the product yield and its catalytic activity.     

Efficient transesterification 4-hydroxytetrahydropyran immobilized lipase resolution of 2-（4-chlorophenyl）- with magnetically separable

We report an efficient kinetic resolution of racemic 2-（4-chlorophenyl）-4-hydroxytetrahydro-pyran （CLP-4-HTHP） via Pseudomonas cepacia lipase （PSL）-catalyzed transesterification, where PSL is immobilized on a core-shell MnFe204@SiO2-（CH2）3-NH2 carrier and used as a magnetically separable catalyst. The as-synthesized PSL/MnFe204@SiO2-（CH2）3-NH2 catalyst exhibits enhanced catalytic activity for resolving racemic CLP-4-HTHP to the corresponding optically pure （2R,4S）-CLP-4-HTHP compared to the free PSL. The ees for the former is 2.3 times larger than that for the latter under optimized conditions （99.4% and 44.1%, respectively）, although the eep for them are same （99.2%）. Meanwhile, the PSL/MnFe204@SiO2-（CH2）3-NH2 catalyst possesses a high saturate magnetization of 59.7 emu/g and could be easily recovered by magnetic separation and reused. The catalytic activity in six recycling tests did not significantly decrease, suggesting its great potential for industrial applications.     

ZnAl2O4 SiO2纳米复合催化剂用于无溶剂条件下乙酸酐与醇、酚和胺的乙酰化反应简

A ZnAl₂O₄@SiO₂ nanocomposite was prepared from metal nitrates and tetraethyl orthosilicate by the sol-gel process, and characterized by X-ray diffraction, Fourier transform infrared, transmission electron microscopy, and N₂ adsorption-desorption measurements. The nanocomposite was tested as a heterogeneous catalyst for the acetylation of alcohols, phenols, and amines under solvent-free conditions. Under optimized conditions, efficient acetylation of these substrates with acetic anhydride over the ZnAl₂O₄@SiO₂ nanocomposite was obtained. Acetylation of anilines and primary aliphatic amines proceeded rapidly at room temperature, while the reaction time was longer for the acetylation of alcohols and phenols, showing that an amine NH₂ group can be selectively acetylated in the presence of alcoholic or phenolic OH groups. The catalyst can be reused without obvious loss of catalytic activity. The catalytic activity of the ZnAl₂O₄@SiO₂ nanocomposite was higher than that of pure ZnAl₂O₄. The method gives high yields, and is clean, cost effective, compatible with substrates having other functional groups and it is suitable for practical organic synthesis.     

H3PMo12O40‐immobilized chitosan/Co3O4: A novel and recyclable nanocomposite for the synthesis of pyrimidinedione derivatives

An efficient three‐component reaction of aromatic aldehydes, 6‐aminouracil/6‐amino‐1,3‐dimethyluracil and 4‐hydroxycoumarin in the presence of a novel heterogeneous catalyst H₃PMo₁₂O₄₀‐immobilized Co₃O₄/chitosan led to a synthesis of a new class of pyrimidinedione derivatives under reflux conditions. The magnetically recoverable nanocomposite of Co₃O₄/chitosan/H₃PMo₁₂O₄₀ was fully characterized by Fourier transform‐infrared spectrophotometry, scanning electron microscopy, X‐ray powder diffraction, energy‐dispersive X‐ray spectroscopy, vibrating‐sample magnetometry and N₂ adsorption–desorption by Brunauer–Emmett–Teller analysis. Results show that Keggin‐type 12‐molybdophosphoric acid immobilized into the network of the cross‐linked chitosan with super‐paramagnetic Co₃O₄ nanoparticles. The present method offers several advantages, such as simple procedure, short reaction times and excellent yields of products. The novelty of the catalyst, high catalytic activity, easy separation from the reaction with an external magnetic field and reusability of the catalyst in six consecutive runs are additional eco‐friendly attributes of this catalytic system.     

Mn(III)‐salan/graphene oxide/magnetite nanocomposite as a highly selective catalyst for aerobic epoxidation of olefins

A nanocomposite was synthesized using carbon‐coated Fe₃O₄ nanoparticle‐decorated reduced graphene oxide as a convenient and efficient supporting material for grafting of a manganese–reduced Schiff base (salan) complex via covalent attachment. The nanocomposite was characterized using X‐ray diffraction, Fourier transform infrared and diffuse reflectance UV–visible spectroscopies, inductively coupled plasma atomic emission spectrometry and scanning electron microscopy. It was evaluated as a catalyst for the aerobic epoxidation of olefins in acetonitrile in combination with a sacrificial co‐reductant (isobutyraldehyde). The catalytic performance of the heterogeneous system of the Mn–salan complex is superior to that of the homogeneous one. The catalyst activity strongly depends on the reaction temperature and nature of the solvent. The epoxide yield increases with the nucleophilic character of the olefin. The nanocomposite performs well as an epoxidation catalyst for electron‐rich and conjugated olefins. It can be recovered from the reaction medium by magnetic decantation and reused, maintaining good catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.     

Efficient catalytic degradation of single and binary azo dyes by a novel triple nanocomposite of Mn3O4/Ag/SiO2

The strategy of structurally integrating noble metal and metal oxides is expected to offer exceptional opportunities toward emerging functions of all. We report the creation of an efficient hetero-structured nanocatalyst consisting of Mn₃O₄ core, SiO₂ shell impregnated with noble Ag nanoparticles. The triple nanocatalyst Mn₃O₄/Ag/SiO₂ was synthesized by using a facile three-step approach to disperse Ag nanoparticles between the surfaces of functionalized Mn₃O₄ and SiO₂. The physicochemical structural characterization was performed by XRD and FTIR. The surface morphologies were observed by SEM and TEM. The EDX measurements confirmed the composition of the composite. The nanocomposite has been used as a catalyst for the degradation of Direct blue 78 in the presence of sodium borohydride (NaBH₄). It has a drastic catalytic effect as compared to Mn₃O₄/Ag and Mn₃O₄. The rate constant of Direct blue 78 reduction followed the order: Mn₃O₄/Ag/SiO₂ (0.25166 min⁻¹) > Mn₃O₄/Ag (0.07971 min⁻¹) > Mn₃O₄ (0.00947 min⁻¹). The effects of different reaction conditions of the catalytic reaction have been determined. The catalytic activity of the as- synthesized nanocomposite was examined for the binary dyes system by incorporation of an additional dye (Sunset yellow). Its influence on the degradation rate and efficiency of Direct blue 78 was investigated. The nanocatalyst exhibited excellent catalytic activity towards the complete degradation of both the Direct blue 78 and Sunset yellow. The degradation percentage for these dyes reached 99.33 and 94.68%, respectively. The recovery and reusability of the Mn₃O₄/Ag/SiO₂ nanocomposite was studied in the reduction reaction of Direct blue 78. Five consecutive recovery reaction cycles were performed. They revealed high stability and constant efficiency of the catalyst for four cycles.     

Preparation and characterization of a silica‐based magnetic nanocomposite and its application as a recoverable catalyst for the one‐pot multicomponent synthesis of quinazolinone derivatives

An environmentally benign magnetic silica‐based nanocomposite (Fe₃O₄/SBA‐15) as a heterogeneous nanocatalyst was prepared and characterized using Fourier transform infrared and ultraviolet–visible diffuse reflectance spectroscopies, scanning electron microscopy, X‐ray diffraction, vibrating sample magnetometry and Brunauer–Emmett–Teller multilayer nitrogen adsorption. Its catalytic activity was investigated for the one‐pot multicomponent synthesis of 2,3‐dihydroquinazolin‐4(1H)‐ones starting from isatoic anhydride, ammonium acetate and various aldehydes under mild reaction conditions and easy work‐up procedure in refluxing ethanol with good yields. The nanocatalyst can be recovered easily and reused several times without significant loss of catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Comparative assessment of the ability of a microwave absorber nanocatalyst in the microwave-assisted biodiesel production process

In this study, a carbon-supported KOH/Ca₁₂Al₁₄O₃₃ nanocomposite was fabricated via the microwave combustion method, in which dextrose was used as a carbon source, and its activity in the microwave-assisted transesterification reaction as a microwave absorption material was assessed. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry, Brunauer–Emmett–Teller (BET), field-emission scanning electron microscopy, and energy dispersive X-ray analyses. The results showed that the carbonate and noncarbonate samples had a calcium aluminate (Ca₁₂Al₁₄O₃₃) structure as a support. Different carbon groups were formed during preparation of the carbon-supported KOH/Ca₁₂Al₁₄O₃₃ nanocomposite, which improved its surface area and porosity. Although the samples presented similar basicity, the carbonated nanocomposite exhibited twice as much activity as the KOH/Ca₁₂Al₁₄O₃₃ nanocatalyst for conversion of canola oil to biodiesel in the microwave-assisted transesterification reaction at 270 W microwave power. The nanocomposite with a larger pore size made active sites easily accessible and exhibited higher catalytic ability where the conversion of 98.8% was obtained under the optimized conditions of 270 W microwave power, methanol/oil molar ratio of 15, 4 wt% of the nanocomposite, and 30 min of reaction time. The carbon-supported nanocatalyst can be reused for at least four times with less reduction in activity. Furthermore, the obtained biodiesel showed that it met the standard values (EN 14214 and ASTM D-6751) with respect to the density, kinematic viscosity at 40 °C, acid number, and flash point.     

White tea extract modified green synthesis of magnetite supported Ag nanoparticles: Evaluation of its catalytic activity,antioxidant and anti-colon cancer effects

In this study, an eco-friendly and low-cost procedure for the synthesis of White tea plant extract modified magnetic nanocomposite (Fe₃O₄@W.tea) has been demonstrated. Ag nanoparticles (Ag NPs) were further decorated in situ over the designed Fe₃O₄@W.tea nanocomposite exploiting the plant derived phytochemicals as bio-reductant and stabilizer. The resulting Fe₃O₄@W.tea/Ag nanocomposite was characterized by various analytical methods like Fourier Transformed Infra Red (FT-IR) spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), energy dispersive X-ray analysis (EDX) elemental mapping, transmission electron microscopy (TEM), vibrating-sample magnetometer (VSM), X-ray diffraction analysis (XRD), and inductively coupled plasma-atomic emission spectrometry (ICP-AES) analysis. The as-synthesized bio-nanomaterial was used as an excellent heterogeneous and magnetically retrievable catalyst in the three-component condensation of 4-hydroxycoumarin, malononitrile and various aldehydes in refluxing aqueous media. A broad range of aromatic aldehydes underwent the reaction to produce diverse pyrano[3,2-c]chromene derivatives in very good yields irrespective of the nature of bearing functional groups or their respective geometrical positions. Due to superparamagnetic character, the material was easily magnetically decanted out and recycled for 8 successive times with preservation of its catalytic activity. After the chemical applications we also explored the material biologically in the resistance of human colon cancer and thereby studied the cytotoxicity over two standard cell lines, HT-29 and Caco-2. The conventional MTT assay was carried out over them which revealed an increase in % cell viability dose dependently. The IC₅₀ values observed in the two cell lines were 384.2 μg/ml and 254.6 μg/ml respectively. In addition, DPPH radical scavenging test was performed for studying anti-oxidant activity. The results validate the administration of Fe₃O₄@W.tea/Agnanocomposite as a competent colon protective drug in the clinical trial studies over human.