Immobilization of Metalloporphyrin on Functionalized MCM-48 Nanoporous Silica as a Catalyst in Oxidation of Cyclohexene: The Effects of Nanoporous Structure of MCM-48 on Its Catalytic Efficiency

MCM-48 nanoporous silica were prepared by the sol–gel method and functionalized by pyridine using a silane agent. With the aid of pyridines on the surface, the nanoporous material was used as a support for immobilization of metalloporphyrin. The formation of this material was confirmed by infrared spectroscopy, X-ray powder diffraction, transmission electron microscopy, inductively coupled plasma atomic emission spectroscopy analysis and specific surface area measurement. The application of this metalloporphyrin-immobilized MCM-48 was investigated as a heterogeneous catalyst in cyclohexene oxidation. Various parameters such as solvent and time were optimized. Also the effect of nanoporous structure on the efficiency of the catalyst was investigated by comparing the results with the same composite using nonporous silica (SiO₂). The result showed that the MCM-48 immobilized metalloporphyrin is a better catalyst for cyclohexene oxidation, which can be attributed to its nanoporous structure. The nanoporous structure increases the surface area of MCM-48 and leads to more metalloporphyrin immobilization.     

Molybdenum Schiff Base Complex Covalently Anchored to Silica-Coated Cobalt Ferrite Nanoparticles as a Novel Heterogeneous Catalyst for the Oxidation of Alkenes

Abstract  

Silica-coated cobalt ferrite nanoparticles were prepared and functionalized with Schiff base groups to yield immobilized bidentate ligands. The functionalized magnetic nanoparticles were then treated with Mo (O₂)₂(acac)₂, resulting in the novel immobilized molybdenum Schiff base catalyst. The as-prepared catalyst was characterized by X-ray powder diffraction, transmission electron microscopy, vibrating sample magnetometry, thermogravimetric analysis, Fourier transform infrared, and inductively coupled plasma atomic emission spectroscopy. The immobilized molybdenum complex was shown to be an efficient heterogeneous catalyst for the oxidation of various alkenes using t-BuOOH as oxidant. This catalyst, which is easily recovered by simple magnetic decantation, could be reused several times without significant degradation in catalytic activity.     

Modification of Magnetite Cellulose Nanoparticles via Click Reaction for use in Controlled Drug Delivery

Superparamagnetic Fe₃O₄ nanoparticles (MNPs) were functionalized by modified cellulose. The modified cellulose was synthesized through bromoacetylation of cellulose (BACell) followed by the substitution of sodium azide to form BACell-N₃. The remaining methylene bromide groups on BACell-N₃ was further reacted with the MNPs to form Fe₃O₄/Cell-N₃. Then propargyl alcohol (PA) was immobilized on the azide-terminated Fe₃O₄ nanoparticles through copper (I)-catalyzed azide-alkyne cycloaddition (click reaction) to form Fe₃O₄/Cell/TAA nanoparticles. Doxorubicin (DOX) was loaded on prepared nanoparticles and release profiles of the DOX as a model drug from the Fe₃O₄/Cell/TAA nanoparticles and its loading capacity were determined by UV–Vis absorption at λ_max 483?nm.     

Preparation of chitosan‐coated magnetite nanoparticles and application for immobilization of laccase

In this study, immobilization of laccase (L) enzyme on magnetite (Fe₃O₄) nanoparticles was achieved, so that the immobilized enzyme could be used repeatedly. For this purpose, Fe₃O₄ nanoparticles were coated and functionalized with chitosan (CS) and laccase from Trametes versicolor was immobilized onto chitosan‐coated magnetic nanoparticles (Fe₃O₄‐CS) by adsorption or covalent binding after activating the hydroxyl groups of chitosan with carbodiimide (EDAC) or cyanuric chloride (CC). For chitosan‐coated magnetic nanoparticles, the thickness of CS layer was estimated as 1.0–4.8 nm by TEM, isoelectric point was detected as 6.86 by zeta (ζ)‐potential measurements, and the saturation magnetization was determined as 25.2 emu g^?1 by VSM, indicating that these nanoparticles were almost superparamagnetic. For free laccase and immobilized laccase systems, the optimum pH, temperature, and kinetic parameters were investigated; and the change of the activity against repeated use of the immobilized systems were examined. The results indicated that all immobilized systems retained more than 71% of their initial activity at the end of 30 batch uses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Immobilization of copper(II)-poly(N-vinylimidazole) complex on magnetic nanoparticles and its catalysis of oxidative polymerization of 2,6-dimethylphenol in water

Poly(N-vinylimidazole) (PVI) was grafted onto magnetic Fe₃O₄ nanoparticles through siloxane bonds to produce PVI-grafted Fe₃O₄ nanoparticles (shortened as Fe₃O₄-g-PVI). The amount of imidazolyl groups in Fe₃O₄-g-PVI was estimated to be 1.16 mmol/g by elemental analysis and thermal gravimetric analysis. The Fe₃O₄-g-PVI coordinated with Cu(II) to form the immobilized Cu(II)-PVI complex. The stoichiometric ratio between imidazolyl groups in Fe₃O₄-g-PVI and Cu(II) was found to be 4 and the complex formation constant (K) was calculated to be 5.6 × 10¹⁴ mol⁻⁴ L⁴. The immobilized Cu(II)-PVI complex was employed to catalyze the oxidative polymerization of 2,6-dimethylphenol (DMP) in water and showed excellent C O/C C selectivity to form PPO. After polymerization, the immobilized Cu(II)-PVI complex catalyst was collected by an external magnetic field and reused in the next run with additional immobilized catalyst and copper ions. After three runs of oxidative polymerization of DMP, the recovery rate of the immobilized Cu(II)-PVI catalyst was above 95% and the yield of PPO maintained as high as 79.2% with the addition of supplementary catalysts. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Selective Allylic oxidation of Cyclohexene by a Magnetically Recoverable Cobalt Oxide Catalyst

Abstract  

In this work, we prepared a new magnetically recoverable CoO catalyst through the deposition of the catalytic active metal nanoparticles of 2–3 nm on silica-coated magnetite nanoparticles to facilitate the solid separation from liquid media. The catalyst was fully characterized and presented interesting properties in the oxidation of cyclohexene, as for example, selectivity to the allylic oxidation product. It was also observed that CoO is the most active species when compared to Co²⁺, Co₃O₄ and Fe₃O₄ in the catalytic conditions studied.     

Preparation of Pt nanoparticle-loaded three-dimensional Fe3O4/carbon with high electro-oxidation activity

A three-dimensional (3D) Fe₃O₄/carbon material functionalized with amino and hydroxyl groups was synthesized by decomposing 2,4,5-trichlorophenol/ferrocene mixture in the presence of ammonia and polyethylene glycol in solvothermal conditions at 250 °C for 30 h by a one-step process. The 3D Fe₃O₄/carbon materials can be loaded with Pt nanoparticles without adding any reducing agent; Pt-loaded 3D Fe₃O₄/carbon hybrid materials have superior electrochemical catalytic activity toward methanol oxidation and the oxidation current density on them is nearly triple that on a commercial Pt/C catalyst.     

Synthesis of a Fe3O4-rGO-ZnO-catalyzed photo-Fenton system with enhanced photocatalytic performance

In this work, we designed a magnetically-separable Fe₃O₄-rGO-ZnO ternary catalyst, ZnO anchored on the surface of reduced graphene oxide (rGO)-wrapped Fe₃O₄ magnetic nanoparticles, where rGO, as an effective interlayer, can enhance the synergistic effect between ZnO and Fe₃O₄. The effects of three operational parameters, namely irradiation time, hydrogen peroxide dosage, and the catalyst dosage, on the photo-Fenton degradation of methylene blue and methyl orange were investigated. The results showed that the Fe₃O₄-rGO-ZnO had great potential for the destruction of organic compounds from wastewater using the Fenton chemical oxidation method at neutral pH. Repeatability of the photocatalytic activity after 5 cycles showed only a tiny drop in the catalytic efficiency.     

pH Responsive Behavior of Fe3O4@PDEA-PEGMA Core-Shell Hybrid Magnetic Nanoparticles

Fe₃O₄@PDEA-PEGMA core-shell magnetic nanoparticles were prepared via surface-initiated atom transfer radical polymerization (ATRP). First, an ATRP initiator was immobilized onto the surface of Fe₃O₄ magnetic nanoparticles, then poly[2-(diethylamino)ethyl methacrylate] (PDEA) and poly(poly[(ethylene glycol) monomethacrylate]) (PEGMA) were grafted from the surface of the magnetic nanoparticles in succession. Each step of the reactions gave distinctive thermogravimetric analysis curves. Polymer shells cleaved from Fe₃O₄ core were measured by gel permeation chromatography, while its molecular weight was found to increase with successive polymerization (with a polydispersity of approximately 1.3–1.4). The architecture of the core-shell nanoparticles was confirmed by transmission electron microscopy. The Fe₃O₄@PDEA-PEGMA hybrid magnetic nanoparticles formed stable dispersions in H₂O at low pH (pH < 6) and precipitated out at high pH (pH > 6). This pH transition behavior was also observed in dynamic light scattering experiments.     

Supported Gold Nanoparticles Catalysts for Solvent-free Selective Oxidation of Benzylic Compounds into Ketones at 1 atm O2

Supported gold nanoparticles catalyst (Au/TiO₂) was investigated for the oxidation of benzylic compounds into corresponding ketones without any organic solvent at 1 atm O₂ under mild reaction conditions (≤100 °C). For instance, indan was oxidized with conversion of 46% and 1-indanone selectivity of 90% at 90 °C for 24 h. Effect of various reaction parameters viz., temperature, time, and effect of a range of supports was studied for the oxidation of indan. The conversion of indan and selectivity of 1-indanone over recycled catalyst remains almost same.     

Size‐Dependent Catalytic Activity of Supported Palladium Nanoparticles for Aerobic Oxidation of Alcohols

Silica‐alumina (SiO₂‐Al₂O₃)‐supported palladium catalysts prepared by adsorption of the tetrachloropalladate anion (PdCl₄²⁻) followed by calcination and reduction with either hexanol or hydrogen were studied for the aerobic oxidation of alcohols. The mean size of the Pd particles over the SiO₂‐Al₂O₃ support was found to depend on the Si/Al ratio, and a decrease in the Si/Al ratio resulted in a decrease in the mean size of the Pd nanoparticles. By changing the Si/Al ratio, we obtained supported Pd nanoparticles with mean sizes ranging from 2.2 to 10 nm. The interaction between the Pd precursor and the support was proposed to play a key role in tuning the mean size of the Pd nanoparticles. The Pd/SiO₂‐Al₂O₃ catalyst with an appropriate mean size of Pd particles could catalyze the aerobic oxidation of various alcohols to the corresponding carbonyl compounds, and this catalyst was particularly efficient for the solvent‐free conversion of benzyl alcohol. The intrinsic turnover frequency per surface Pd atom depended significantly on the mean size of Pd particles and showed a maximum at a medium mean size (3.6–4.3 nm), revealing that the aerobic oxidation of benzyl alcohol catalyzed by the supported Pd nanoparticles was structure‐sensitive.     

Functional acrylic acid as stabilizer for synthesis of smart hydrogel particles containing a magnetic Fe3O4 core

This paper reports a novel method to synthesize magnetic, stimuli-sensitive latex nanoparticles made with magnetite/poly(N-isopropylacrylamide-co-acrylic acid) (Fe₃O₄/P(NIPAAm-co-AAc)). To form a stabilized suspended core, iron oxide (Fe₃O₄) was functionalized with AAc such that further polymerization with NIPAAm and AAc monomers could occur. The P(NIPAAm-co-AAc) shell layer exhibited thermosensitive properties. The inclusion of Fe₃O₄ into the latex nanoparticles was confirmed using transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction spectroscopy, thermogravimetric analyzer (TGA), and superconducting quantum interference device magnetometer. The NIP–(AAc2.6–Fe) latex nanoparticles contained 2.25% Fe₃O₄ (by weight), as determined by TGA analysis. The particle diameters measured approximately 160–240 nm with a lower critical solution temperature of 35 °C. These novel magnetic stimuli-responsive latex nanoparticles have potential applications in numerous fields, such as catalyst supports, protein immobilization, cancer therapy, target drug delivery systems, and other biomedical applications.     

Facile Synthesis and Catalytic Application of Silver-Deposited Magnetic Nanoparticles

In this work, we have investigated a novel one-step fabrication of Ag-deposited Fe₂O₃ nanoparticles and their application for the catalytic reduction of 4-nitrophenol to 4-aminophenol by NaBH₄. To deposit Ag onto them, Fe₂O₃ particles were dispersed in a reaction mixture consisting of ethanolic AgNO₃ and butylamine, and then the reaction mixture was incubated and shaken for 40 min at 45 °C. With this simple and surfactant-free fabrication of Ag-deposited Fe₂O₃ nanoparticles, we can avoid contamination in the final product, which makes them suitable for further catalytic applications. Since the magnetic particles are readily recovered from the solution phase without centrifugation and/or filtering, the Ag-deposited Fe₂O₃ nanoparticles prepared in this work have been exploited as solid phase catalysts for the reduction of 4-nitrophenol in the presence of NaBH₄. At the end of the reaction, the Ag-deposited Fe₂O₃ catalyst particles still remain active. They can thus be separated from the product, 4-aminophenol, simply using a neodium magnet and can be recycled a number of times.     

Synthesis and Characterization of Magnetically Retrievable Fe3O4/Polyvinylpyrrolidone/Polystyrene Nanocomposite Catalyst for Efficient Catalytic Oxidation Degradation of Dyes Pollutants

Recently, the application of metal oxides such as Fe₃O₄ nanoparticles have wide interest for environmental remediation and treatment of wastewater especially contaminated with azo dyes owing to its high degradation efficacy and low toxicity. The recovery of magnetic catalysts without losing their efficiency is an essential feature in the catalytic applications. The aim of this article is to investigate and synthesis of magnetically retrievable Fe₃O₄/polyvinylpyrrolidone/polystyrene (Fe₃O₄/PVP/PS) nanocomposite for the catalytic degradation of azo dye acid red 18 (AR18). Fe₃O₄/PVP/PS nanocomposite was prepared in two steps. Firstly, PVP/PS microsphere was synthesized by γ-irradiation polymerization of styrene in presence of PVP solution. Secondly, deposition of Fe₃O₄ nanoparticles on PVP/PS microsphere was achieved by the alkaline co-precipitation of Fe³⁺/Fe²⁺ ions. The chemical structural and morphological properties of PVP/PS microsphere and Fe₃O₄/PVP/PS nanocomposite were examined by XRD, TEM, DLS, FTIR, EDX and VSM techniques. TEM results showed homogeneous morphology, spherical shaped and well-dispersed Fe₃O₄ nanoparticles with average particle size of 26 nm around PVP/PS microspheres. The VSM measurements of Fe₃O₄/PVP/PS nanocomposite exhibit excellent magnetic response of saturation magnetization 26.38 emu/g which is suitable in magnetic separation. The effect of the synthesized Fe₃O₄/PVP/PS nanocomposite on the catalytic degradation of AR18 in presence of hydrogen peroxide (H₂O₂) as a heterogeneous Fenton-like catalyst was examined. The catalyst Fe₃O₄/PVP/PS/H₂O₂ played basic role in promoting the oxidation degradation efficiency of AR18 of initial concentration 50 mg/L to 94.4% in 45 min with excellent recyclability till the sixth cycles under the best conditions of pH 3, 2% v/v H₂O₂ and 0.3 g catalyst amount. Furthermore, the Fe₃O₄/PVP/PS/H₂O₂ hybrid catalyst system supports high capability for oxidation degradation of mixture of different dyes. The Fe₃O₄/PVP/PS nanocomposite catalyst had high magnetic and recyclability characters which are acceptable for the treatment of wastewater contaminated by various dyes pollutants.

     

Immobilization of Candida antarctica lipase onto cellulose acetate-coated Fe2O3 nanoparticles for glycerolysis of olive oil

Candida antarctica lipase was covalently immobilized onto the surface of cellulose acetate-coated Fe₂O₃ nanoparticles. The characterizations of immobilized lipase were examined by Fourier transform infrared spectrophotometer (FTIR) and field emission gun-scanning electron microscopy (FEG-SEM). The immobilized lipase was assayed for production of monoglycerides (MG) and diglycerides (DG) by glycerolysis of olive oil in a solvent medium. The effect of various reaction conditions on the MG and DG production such as reaction time, temperature, the molar ratio of glycerol to oil and amount of immobilized lipase was investigated. The optimum condition for MG and DG production was found at 50 °C temperature and 0.025 g of lipase with the molar ratio of glycerol to oil 1.5: 1 in 5 h of reaction time. The effect of substrate concentration on enzymatic activity of the free and immobilized lipase showed the best fits to the Lineweaver-Burk plots. The K _m and V _max values of immobilized lipase were found to be 25mM and 0.58mM/min, whereas that for free lipase was 52.63mM and 1.75mM/min, respectively. The activation and deactivation energy was found to decrease for immobilization of lipase on cellulose acetate-coated Fe₂O₃ nanoparticles.     

Synthesis of ZnFe2O4 Nanoparticles Confined Within Nanoporous Silica Using Trinuclear Oxo-centered Complex: Inorganic Complexes as a Precursor for the Preparation of Magnetic Nanoporous Silica

MCM-48 Nanoporous silica (Mobil Composition of Matter, #48) was synthesized and functionalized by pyridine groups. The formation of this functionalized nanoporous silica was confirmed by elemental analysis, low angle x-ray powder diffraction and N₂ adsorption. The trinuclear oxo-centered Fe₂Zn(μ₃-O)(CF₃COO)₆(H₂O)₃ cluster was synthesized and immobilized inside the pyridine functionalized MCM-48 pores. The immobilization of this cluster was confirmed by IR spectroscopy and flame atomic adsorption spectroscopy. Fe₂ZnO₄ nanoparticles were confined within the nanoporous silica pores by thermolysis of the immobilized Fe₂Zn(μ₃-O)(CF₃COO)₆(H₂O)₃ cluster and were characterized by high angle X-ray powder diffraction and high resolution transmission electron microscopy. This method is suitable for the one-pot preparation of Fe₂ZnO₄ confined nanoporous silica.     

A novel platform of hemoglobin on core–shell structurally Fe3O4@Au nanoparticles and its direct electrochemistry

A novel platform, which hemoglobin (Hb) was immobilized on core–shell structurally Fe₃O₄/Au nanoparticles (simplified as Fe₃O₄@Au NPs) modified glassy carbon electrode (GCE), has been developed for fabricating the third biosensors. Fe₃O₄@Au NPs, characterized using transmission electron microscope (TEM), scanning electron microscope (SEM) and energy dispersive spectra (EDS), were coated onto GCE mediated by chitosan so as to provide larger surface area for anchoring Hb. The thermodynamics, dynamics and catalysis properties of Hb immobilized on Fe₃O₄@Au NPs were discussed by UV–visible spectrum (UV–vis), electrochemical impedance spectroscopy (EIS), electrochemical quartz crystal microbalance technique (EQCM) and cyclic voltammetry (CV). The electrochemical parameters of Hb on Fe₃O₄@Au NPs modified GCE were further carefully calculated with the results of the effective working area as 3.61 cm², the surface coverage concentration (Γ) as 1.07 × 10⁻¹² mol cm⁻², the electron-transfer rate constant (K_s) as 1.03 s⁻¹, the number of electron transferred (n) as 1.20 and the standard entropy of the immobilized Hb (ΔS⁰′) as calculated to be −104.1 J mol⁻¹ K⁻¹. The electrocatalytic behaviors of the immobilized Hb on Fe₃O₄@Au NPs were applied for the determination of hydrogen peroxide (H₂O₂), oxygen (O₂) and trichloroacetic acid (TCA). The possible functions of Fe₃O₄ core and Au shell as a novel platform for achieving Hb direct electrochemistry were discussed, respectively.     

Production of Galactooligosaccharides Using β-Galactosidase Immobilized on Chitosan-Coated Magnetic Nanoparticles with Tris(hydroxymethyl)phosphine as an Optional Coupling Agent

β-Galactosidase was immobilized on chitosan-coated magnetic Fe₃O₄ nanoparticles and was used to produce galactooligosaccharides (GOS) from lactose. Immobilized enzyme was prepared with or without the coupling agent, tris(hydroxymethyl)phosphine (THP). The two immobilized systems and the free enzyme achieved their maximum activity at pH 6.0 with an optimal temperature of 50 °C. The immobilized enzymes showed higher activities at a wider range of temperatures and pH. Furthermore, the immobilized enzyme coupled with THP showed higher thermal stability than that without THP. However, activity retention of batchwise reactions was similar for both immobilized systems. All the three enzyme systems produced GOS compound with similar concentration profiles, with a maximum GOS yield of 50.5% from 36% (w·v⁻¹) lactose on a dry weight basis. The chitosan-coated magnetic Fe₃O₄ nanoparticles can be regenerated using a desorption/re-adsorption process described in this study.     

Cr(III)‐containing Fe3O4/mercaptopropanoic acid‐poly(2‐hydroxyethyl acrylate) nanocomposite: Highly active magnetic catalyst for direct hydroxylation of benzene

In this study, polymer‐grafted magnetic nanoparticles containing chromium(III) ions incorporated onto Fe₃O₄/mercaptopropanoic acid‐poly(2‐hydroxyethyl acrylate) was prepared via a simple and in situ method. The obtained magnetic nanocomposite exhibited high catalytic activity and excellent selectivity in direct hydroxylation of benzene in the presence of hydrogen peroxide under solvent‐free condition. The magnetic catalyst could be also separated by an external magnet and reused seven times without any significant loss of activity/selectivity. Due to the Lewis acidity of the Fe³⁺ groups in the structure of magnetic nanoparticles, the high efficiency of this catalyst is possibly due to the synergetic effect of Cr³⁺ and Fe³⁺ groups in the structure of magnetic nanocomposite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40383.     

Carbon Nanoparticles on Magnetite: A New Heterogeneous Catalyst for the Oxidation of 5-Hydroxymethylfurfural (5-HMF) to 2,5-Diformoylfuran (DFF)

Development of new materials for catalytic applications is one of the rapidly growing research areas. The selective oxidation of 5-hydroxymethyl furfural (HMF) to 2,5-diformylfuran (DFF) is one of the rapidly growing research area due to having its own importance in the fuel technology. We report a new heterogeneous catalyst for the oxidation of HMF to DFF in aqueous medium using a carbon soot (from candle light) deposited on magnetite (Fe₃O₄@C). Further, the potentiality of our catalyst has also been realized in direct production of DFF from biomass (using either fructose or glucose) with high conversions via two consecutive steps involving dehydration and oxidation. Further, proved that Fe₃O₄@C plays a major role in the dehydration of sugar molecules whereas Fe₃O₄ alone could not.