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1.
The simple preparation of catalysts with superior catalytic activity and good reusability is highly desirable. Herein, we report a novel strategy to construct reduced graphene oxide (rGO)/Pd–Fe3O4@polypyrrole (PPy) catalysts with Pd and Fe3O4 nanoparticles anchored on a rGO nanosheet surface and wrapped in a PPy shell. The synthesis and assembly of both the Pd and Fe3O4 nanoparticles, the preparation of the PPy layer, and the reduction of graphene oxide nanosheets were finished in one step. In the system, the PPy layer not only prevented aggregation of Pd and Fe3O4 nanoparticles, but also generated a synergistic effect with precursor Pd2+ ions, which led to a high dispersity of as‐prepared Pd nanoparticles. Although the procedure was simplified to one step, the catalytic activity and reusability were not sacrificed. In the reduction of 4‐nitrophenol, their catalytic performance was better than that in recent reports. Moreover, the catalysts showed good reusability owing to their magnetic properties.  相似文献   

2.
A strategy has been developed for the synthesis, characterization and catalysis of magnetic Fe3O4/P(GMA‐EGDMA)‐NH2/HPG‐COOH‐Pd core‐shell structure supported catalyst. The P(GMA‐EGDMA) polymer layer was coated on the surface of hollow magnetic Fe3O4 microspheres through the effect of KH570. The core‐shell magnetic Fe3O4/P(GMA‐EGDMA) modified by ‐NH2 could be grafted with HPG. Then, the hyperbranched glycidyl (HPG) with terminal ‐OH were modified by ‐COOH and adsorbed Pd nanoparticles. The hyperbranched polymer layer not only protected the Fe3O4 magnetic core from acid–base substrate corrosion, but also provided a number of functional groups as binding sites for Pd nanoparticles. The prepared catalyst was characterized by UV–vis, TEM, SEM, FTIR, TGA, ICP‐OES, BET, XRD, DLS and VSM. The catalytic tests showed that the magnetic Fe3O4/P(GMA‐EGDMA)‐NH2/HPG‐COOH‐Pd catalyst had excellent catalytic performance and retained 86% catalytic efficiency after 8 consecutive cycles.  相似文献   

3.
In this paper, a simple route for palladium (Pd) nanoparticles attached to the surface of hollow magnetic Fe3O4/P (GMA‐DVB)‐polyethyleneimine (PEI) microspheres was established. Due to the large amount of imidogen groups and tertiary amine groups presenting in the PEI, Pd2+ ions could be anchored to the support by complexation with a polyfunctional organic ligand. Thereafter, a magnetic Pd catalyst having a high loading amount and good dispersibility was obtained by reducing Pd2+ ions. Afterwards, the prepared catalyst was characterized by TEM, SEM, FTIR, XRD, TGA, VSM, and UV–vis in detail. Ultimately, their catalytic activity was evaluated using the reduction of 4‐nitrophenol (4‐NP). Research showed that the Fe3O4/P (GMA‐DVB)‐PEI/Pd catalyst possessed high catalytic performances for the reduction of 4‐NP with a conversion rate of 98.43% within 540 s. Furthermore, the catalyst could be easily recovered and reused at least for nine successive cycles.  相似文献   

4.
A novel chiral magnetic nanocatalyst was prepared by the surface modification of Fe3O4 magnetic nanoparticles (MNPs) with a chloropropylsilane and further by arginine to form Fe3O4@propylsilan‐arginine (Fe3O4@PS‐Arg). After the structural confirmation of Fe3O4@PS‐Arg synthesized MNPs by Fourier transform‐infrared, X‐ray diffraction, field emission‐scanning electron microscopy, transmission electron microscopy, vibrating‐sample magnetometry and thermogravimetric analyses, their catalytic activity was evaluated for one‐pot enantioselective synthesis of 3‐amino‐1‐aryl‐1H‐benzo[f]chromene‐2‐carbonitrile derivatives. The results showed that in the presence of 0.07 g Fe3O4@PS‐Arg nanocatalyst and ethanol as solvent, the best reaction yield (96%) was obtained in the least time (5 min). Easy operation, reusability and stability, short reaction time, high reaction yields and good enantioselectivity are the major advantages of the newly synthesized nanocatalyst. Also, this study provides a novel strategy for further research and investigation on the synthesis of new reusable enantioselective catalysts and chiral compounds.  相似文献   

5.
A robust, safe and magnetically recoverable palladium catalyst was synthesized by anchoring Pd(II) onto ethylenediaminetetraacetic acid‐coated Fe3O4 (Fe3O4@EDTA) magnetic nanoparticles. The Fe3O4 magnetic nanoparticle‐supported Pd(II)–EDTA complex catalyst thus obtained was characterized using scanning and transmission electron microscopies, thermogravimetric analysis, vibrating sample magnetometry, X‐ray diffraction, and inductively coupled plasma atomic emission and Fourier transform infrared spectroscopies. Fe3O4@EDTA–Pd(II) was screened for the Suzuki reaction and reduction of nitro compounds in water. The Pd content of the catalyst was measured to be 0.28 mmol Pd g?1. In addition, the Fe3O4@EDTA–Pd catalyst can be easily separated and recovered with an external permanent magnet. The anchored solid catalyst can be recycled efficiently and reused five times with only a very slight loss of catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

6.
An eco‐efficient one‐pot three component reaction between different aldehydes or ketones with alkynes and amines for the synthesis of propargylamines was performed using Fe3O4@TiO2/Cu2O as a nano‐magnetic composite under solvent free condition. The catalyst showed remarkable catalytic activity by decreasing the time of the reaction in comparison of other reported magnetic catalysts. In addition, the Fe3O4@TiO2/Cu2O can be easily recycled and reutilized for five times without apparent loss of catalytic activity.  相似文献   

7.
Supported palladium catalyst (Pd/Fe3O4@SiO2) was easily prepared by supporting PdCl2 on silica‐coated magnetic nanoparticles Fe3O4 in ethylene glycol. The as‐prepared sample was characterized by infrared spectroscopy (IR), X‐ray diffraction (XRD) and X‐ray photoelectron spectrometer (XPS). The formation of active specie Pd(0) was confirmed by XRD and XPS, and the Pd loading for the fresh and recovered catalyst was determined by atomic absorption spectroscopy (AAS). Pd/Fe3O4@SiO2 was employed for the synthesis of biphenyl derivatives via Suzuki reaction. In terms of the yield of biphenyl, the supported catalyst displayed nearly equal catalytic performance to that of homologous PdCl2 under microwave irradiation for 30 min but higher than that obtained by traditional heating method for 12 h. The catalytic performance of Pd/Fe3O4@SiO2 for Suzuki reactions involving various aryl halides and arylboronic acids were also examined. Impressive yield of biphenyl at 68.2% was obtained even in the presence of unreactive aryl chlorides. Pd/Fe3O4@SiO2 was recovered by a permanent magnet and directly reused in the next run, and no obvious deactivation was observed for up to 6 times. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

8.
Transition metal compounds have emerged as suitable catalysts for organic reactions. Magnetic compounds as soft Lewis acids can be used as catalysts for organic reactions. In this report, the Fe3O4 nanostructures were obtained from Fe2+ and Fe3+-salts, under an external magnetic field (EMF) without any protective agent. The X-ray photoelectron spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy tools were used to characterize these magnetic compounds. The two-dimensional (2-D, it showed nanometric size in the two dimensions, nanorod structure) Fe3O4 compound showed high catalytic activity and stability in N- and C-alkylation reactions. A diverse range of N- and C-alkylation products were obtained in moderate to high yield under green and mild conditions in air. Also the N- and C-alkylation products can be obtained with different selectivity and yield by exposure reactions with EMF. Results of alkylation reactions showed that the presence of Fe(II) and Fe(III) species on the surface of magnetic catalysts (phase structure of magnetic compounds) are essential as very cheap active sites. Also, morphology of magnetic catalysts had influence on their catalytic performances. After the reaction, the catalyst/product(s) separation could be easily achieved with an external magnet and more than 95% of catalyst could be recovered. The catalyst was reused at least four times without any loss of its high catalytic activity for N- and C-alkylation reactions.  相似文献   

9.
Robust nitrogen‐enriched Fe3O4@carbon nanospheres have been fabricated as a catalyst scaffold for Pt nanoparticles. In this work, core–shell Fe3O4@3‐aminophenol/formaldehyde (APF) nanocomposites were first synthesized by a simple hydrothermal method, and subsequently carbonized to Fe3O4@N‐Carbon nanospheres for in situ growth of Pt nanocrystals. Abundant amine groups were distributed uniformly onto Fe3O4@N‐Carbon nanospheres, which not only improved the dispersity and stability of the Pt nanocrystals, but also endowed the Pt‐based catalysts with good compatibility in organic solvents. The dense three‐dimensional cross‐linked carbon shell protects the Fe3O4 cores against damage from harsh chemical environments, even in aqueous HCl (up to 1.0 m ) or NaOH (up to 1.0 m ) solutions under ultrasonication for 24 hours, which indicates that it can be used as a robust catalyst scaffold. In the reduction of nitrobenzene compounds, the Fe3O4@N‐Carbon@Pt nanocatalysts show outstanding catalytic activity, stability, and recoverability.  相似文献   

10.
A new mesoporous organic–inorganic nanocomposite was formulated and then used as stabilizer and support for the preparation of palladium nanoparticles (Pd NPs). The properties and structure of Pd NPs immobilized on prepared 1,4‐diazabicyclo[2.2.2]octane (DABCO) chemically tagged on mesoporous γ‐Fe2O3@hydroxyapatite (ionic modified (IM)‐MHA) were investigated using various techniques. The synergistic effects of the combined properties of MHA, DABCO and Pd NPs, and catalytic activity of γ‐Fe2O3@hydroxyapatite‐DABCO‐Pd (IM‐MHA‐Pd) were investigated for the Heck cross‐coupling reaction in aqueous media. The appropriate surface area and pore size of mesoporous IM‐MHA nanocomposite can provide a favourable hard template for immobilization of Pd NPs. The loading level of Pd in the nanocatalyst was 0.51 mmol g?1. DABCO bonded to the MHA surface acts as a Pd NP stabilizer and can also lead to colloidal stability of the nanocomposite in aqueous solution. The results reveal that IM‐MHA‐Pd is highly efficient for coupling reactions of a wide range of aryl halides with olefins under green conditions. The superparamagnetic nature of the nanocomposite means that the catalyst to be easily separated from solution through magnetic decantation, and the catalytic activity of the recycled IM‐MHA‐Pd showed almost no appreciable loss even after six consecutive runs.  相似文献   

11.
Efficient and reusable nanocatalysts fabricated via a facile assembly are highly desirable for the cost‐effective hydrogenation reduction. Inspired by a fishing process with a fishnet, multifunctional nanostructured catalysts are rationally designed to combine interesting features via the self‐redox assembly of Fe3O4‐Ag composites on reduced graphene oxide (rGO) (Fe3O4‐Ag/rGO). In detail, Fe3O4 nanoparticles (NPs) endow the ternary hybrids with superparamagnetism (21.42 emu g?1), facilitating catalysts to be separated from the reaction system. rGO could provide electron transfer pathways, enhancing catalytic activity. More interestingly, GO and Ag+ could behave as oxidants to oxidize Fe2+ for the in situ assembly of Fe3O4‐Ag/rGO without any addition of reductant/oxidant or organic solvents, and AgNPs endow the ternary hybrids with excellent catalytic behaviour. Meaningfully, the bioinspired process enables the ternary hybrids to possess more abundant micro?/nanopores, larger surface area, and more amorphization. They exhibit exceptional catalytic performance, and could be recycled with excellent activity by means of convenient magnetic separation (at least 7 times). Moreover, the ternary hybrids could degrade methylene blue under UV light due to different valence states of Fe in Fe3O4. Therefore, the proposed bioinspired assembly and structure design for hierarchical catalysts would pave a promising way to assemble other catalysts.  相似文献   

12.
The catalytic activity of l ‐arginine‐coated nano‐Fe3O4 particles (Fe3O4@l ‐arginine) proves they are a novel magnetic catalyst without the use of heat and reflux for the synthesis of 1,3‐diaryl‐2‐N‐azaphenalene derivatives and n‐acyl‐1,3‐diaryl‐2‐N‐azaphenylene derivatives in a one‐pot pseudo‐five‐component condensation reaction of compounds of 2,7‐naphthalene diol, aldehydes, and ammonia derivatives (ammonium acetate or ammonium hydrogen phosphate) and solvent (water and alcohol) with high yield and short reaction times, economical, and simple workup. The structure and magnetic properties of the obtained nanoparticles were characterized via Fourier transform infrared spectroscopy (IR) and field emission scanning electron microscopy (FE‐SEM). The results demonstrated that the average size of the synthesized magnetite nanoparticles is about 21 nm. In addition, the heterogeneous catalyst can be easily recovered magnetically and can be reused for further runs without significant loss of its catalytic activity.  相似文献   

13.
Hierarchical Fe3O4@poly(4‐vinylpyridine‐co‐divinylbenzene)@Au (Fe3O4@P(4‐VP–DVB)@Au) nanostructures were fabricated successfully by means of a facile two‐step synthesis process. In this study, well‐defined core–shell Fe3O4@P(4‐VP–DVB) microspheres were first prepared with a simple polymerization method, in which 4‐VP was easily polymerized on the surface of Fe3O4 nanoparticles by means of strong hydrogen‐bond interactions between ? COOH groups on poly(acrylic acid)‐modified Fe3O4 nanoparticles and a 4‐VP monomer. HAuCl4 was adsorbed on the chains of a P(4‐VP) shell and then reduced to Au nanoparticles by NaBH4, which were embedded into the P(4‐VP) shell of the composite microspheres to finally form the Fe3O4@P(4‐VP–DVB)@Au nanostructures. The obtained Fe3O4@P(4‐VP–DVB)@Au catalysts with different Au loadings were applied in the reduction of 4‐nitrophenol (4‐NP) and exhibited excellent catalytic activity (up to 3025 h?1 of turnover frequency), facile magnetic separation (up to 31.9 emu g?1 of specific saturation magnetization), and good durability (over 98 % of conversion of 4‐NP after ten runs of recyclable catalysis and almost negligible leaching of Au).  相似文献   

14.
Based on the characteristics of polycations of chitosan and glucoamylase, which are oppositely charged, they were successfully alternatingly deposited onto the surface of aldehyde‐modified Fe3O4 nanoparticles by using a layer‐by‐layer ion exchange method to form magnetic carriers to construct multilayer films (designated as Fe3O4@(CS/GA)n). The (CS/GA)n film systems were endowed with the pH‐dependent properties of chitosan as well as the catalytic activity of glucoamylase. The changes in weight loss and surface chemistry, morphology, and magnetic sensitivity were monitored and verified by UV/Vis spectroscopy, zeta potential, TEM, and a vibrating sample magnetometer. Subsequently, the influence of the number of bilayers, storage stability, pH, temperature, and reusability of Fe3O4@(CS/GA)5 biocatalysts on catalytic activity were investigated. The results from characterization and determination remarkably indicate that Fe3O4@(CS/GA)5 presents excellent catalytic activity, storage stability, pH stability, and reusability in comparison with free enzyme. Fe3O4@(CS/GA)5 retained >60 % of its initial activity at 65 °C over 6 h; the optimum temperature and pH also increased to the ranges of 45–65 °C and 2.5–3.5, respectively, and only 27 % activity was lost after 10 cycles. This new strategy simplifies the reaction protocol and improves encapsulation efficiency and catalytic activity for new potential applications in biotechnology.  相似文献   

15.
Nanometer‐sized magnetic stirring bars containing Pd nanoparticles (denoted as Fe3O4‐NC‐PZS‐Pd) for heterogeneous catalysis in microscopic system were prepared through a facile two‐step process. In the hydrogenation of styrene, Fe3O4‐NC‐PZS‐Pd showed an activity similar to that of the commercial Pd/C catalyst, but much better stability. In microscopic catalytic systems, Fe3O4‐NC‐PZS‐Pd can effectively stir the reaction solution within microdrops to accelerate mass transfer, and displays far better catalytic activity than the commercial Pd/C for the hydrogenation of methylene blue in an array of microdroplets. These results suggested that the Fe3O4‐NC‐PZS‐Pd could be used as nanoscale stirring bars in nanoreactors.  相似文献   

16.
Novel Pd nanoparticles were prepared in five successive stages: 1) preparation of the Fe3O4 magnetic nanoparticles (Fe3O4 MNPs), 2) coating of Fe3O4 MNPs with SiO2 (Fe3O4@SiO2), 3) functionalization of Fe3O4@SiO2 with 3‐chloropropyltrimethoxy‐ silane (CPTMS) ligand (Fe3O4@SiO2@CPTMS), 4) further functionalization with 3,5‐diamino‐1,2,4‐triazole (DAT) ligand (Fe3O4@SiO2@CPTMS @DAT), and 5) the complexation of Fe3O4@SiO2@CPTMS@DAT with PdCl2 (Fe3O4@SiO2@CPTMS@ DAT@Pd). Then, the obtained Pd nano‐catalyst characterized by different methods such as the elemental analysis (CHN), FT‐IR, XRD, EDX, SEM, TEM, TG‐DTA and VSM. Finally, the Pd catalyst was applied for the synthesis of various 2‐imino‐3‐phenyl‐2,3‐dihydrobenzo[d]oxazol‐5‐ols.  相似文献   

17.
采用多步法依次将制备的Fe3O4纳米颗粒和Pt纳米颗粒负载到多壁碳纳米管(MCNT)上得到Pt/Fe3O4-MCNT磁性催化剂,以X射线衍射(XRD)、透射电镜(TEM)、超导量子干涉磁强计(SQUID)和热重-差热分析(TG-DTA)对Pt/Fe3O4-MCNT磁性催化剂的结构和磁性质进行了表征。研究发现预制备的Fe3O4纳米颗粒与Pt纳米颗粒均匀地分散于MCNT上,新制备以及多次使用后的Pt/Fe3O4-MCNT室温下都具有良好的超顺磁性。研究了Pt/Fe3O4-MCNT磁性催化剂上的肉桂醛选择性加氢反应,结果显示催化剂具有良好的C=O加氢活性,肉桂醛转化率在50%左右时,肉桂醇选择性可达96%以上。尺寸均一的Pt粒子均匀的分散在催化剂上可能是催化剂具有良好的C=O加氢选择性的重要原因。在外加磁场作用下催化剂可以高效地从液相反应体系中分离,经多次循环使用后仍具有良好的催化性能。  相似文献   

18.
A ferrocene‐based ionic liquid (Fe‐IL) is used as a metal‐containing feedstock with a nitrogen‐enriched ionic liquid (N‐IL) as a compatible nitrogen content modulator to prepare a novel type of non‐precious‐metal–nitrogen–carbon (M‐N‐C) catalysts, which feature ordered mesoporous structure consisting of uniform iron oxide nanoparticles embedded into N‐enriched carbons. The catalyst Fe10@NOMC exhibits comparable catalytic activity but superior long‐term stability to 20 wt % Pt/C for ORR with four‐electron transfer pathway under alkaline conditions. Such outstanding catalytic performance is ascribed to the populated Fe (Fe3O4) and N (N2) active sites with synergetic chemical coupling as well as the ordered mesoporous structure and high surface area endowed by both the versatile precursors and the synthetic strategy, which also open new avenues for the development of M‐N‐C catalytic materials.  相似文献   

19.
Two new Fe3O4 microspheres‐supported semi‐homogeneous catalysts, namely Fe3O4‐G4‐polyaminoamido (PAMAM) dendrimers‐Pd(0) and Fe3O4‐polyethylene glycols (PEGs)‐Pd(0) were synthesized and characterized by X‐ray powder diffraction, infrared spectrum, scanning electron microscopy, transmission electron microscopy, X‐ray photoelectron spectroscopy and thermal gravimetric analysis, which can catalyze Suzuki coupling reactions. The performance of catalysts was tested for the reactions of aryl halides with phenyl boronic acid and compared with a heterogeneous catalyst Fe3O4‐(3‐aminopropyl)triethoxysilane (APTS)‐Pd(0), in which Fe3O4‐G4‐PAMAM dendrimers‐Pd(0) shows the best activity among the three catalysts. The order of the catalytic activities is Fe3O4‐G4‐PAMAM dendrimers‐Pd(0)>Fe3O4‐PEGs‐Pd(0)>Fe3O4‐APTS‐Pd(0). The catalysts can be quickly and completely recovered by simply applying a magnet of 105 mT and the efficiencies remain unaltered even after four recycles.  相似文献   

20.
Conventional solid catalysts for heterogeneous Fenton‐like reactions in bulk solution usually suffer from aggregation and vulnerability, which greatly lower the catalytic efficiency and hamper their practical application. Herein, we demonstrate a promising yolk–shell nanostructure with both the core and the shell composed of magnetite (designated as yolk‐like Fe3O4@Fe3O4/C) as a nanoreactor capable of accommodating the Fenton‐like reaction into its void space. Benefiting from the mesoporous shell and perfect interior cavity of this composite, reactants can access and be abundantly confined within the microenvironment where Fe3O4 sites are dispersed on the entire cavity surfaces, thus leading to a higher catalytic efficiency compared with the conventional solid catalysts in bulk solution. The chosen model reaction of chlorophenols degradation in the presence of the as‐prepared materials as well as hydrogen peroxide (H2O2) confirms this assumption. Under the optimal reaction conditions, more than 97 % 4‐chlorophenol (4‐CP) can be degraded in the Fe3O4@Fe3O4/C nanoreactor, whereas only 28 % can be achieved by using bare Fe3O4 particles within 60 min. Furthermore, owing to the existence of the outermost carbon layer and high‐magnetization properties, the nanoreactor can be re‐used for several runs. The synthesized nanoreactor displays superior catalytic activity toward the Fenton‐like reaction compared with the bare solid catalysts, and thereby holds significant potential for practical application in environmental remediation.  相似文献   

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