Dechlorination of carbon tetrachloride by Nanoscale Nickeled Zero‐Valent Iron @ Multi‐Walled Carbon Nanotubes: Impact of reaction conditions,kinetics and mechanism

The nanoscale nickeled zero‐valent iron @ multi‐walled carbon nanotubes (NF@MWCNTs) were synthesized, characterized and used to dispose carbon tetrachloride (CT) in aqueous solution. Scanning electron microscopy (SEM), X‐ray energy dispersive spectroscopy (EDS), X‐ray diffraction (XRD) and Brunauer–Emmett–Teller (BET) gas sorptometry measurements were conducted to characterize the microstructure of the NF@MWCNTs. And batch experiments under different operation parameters were conducted to investigated the activity of NF@MWCNTs on degrading CT, including the content of NF@MWCNTs composites, temperature, catalyst dosage, initial pH and different anions. The experimental results showed that 4% nickel content of Ni/Fe bimetal and 2:1 doping ratio of Fe/MWCNTs were the wise choices in this study, which provided excellent degradation efficiency of CT when compared with nanoscale zero‐valent iron (nZVI) (97.44% and 55.28%, respectively). That was benefited from the fact that MWCNTs as an excellent support material could reduce the activation energy of 7.952 kJ/mol, and the nickel metal further reduced the reaction activation energy of 11.022 kJ/mol as presented in the conceptual model. Beyond that, NF@MWCNTs showed good reusability after five times consecutive reaction. Based on these, the reaction mechanism and degradation pathway also had been discussed.     

Degradation of carbon tetrachloride using ultrasound‐assisted nanoscaled zero‐valent iron particles@sulfur/nitrogen dual‐doped reduced graphene oxide composite: Kinetics,activation energy,effects of reaction conditions and degradation mechanism

We report a study of the synthesis of nanoscale zero‐valent iron particles stabilized by sulfur/nitrogen dual‐doped reduced graphene oxide (i.e. nZVI@SN‐rGO) and their applications as major reactants for the dechlorination of carbon tetrachloride (CT) by combining sonolysis with consideration of several operation parameters such as pH, temperature, catalyst dosage, as well as in the presence of common inorganic anions. The experimental results showed that the modified technology could remain effective for up to 180 min of reaction time under optimal conditions. Especially, there was no significant reduction in the removal efficiency toward CT even after five cycles, which was indicative of good stability. A study of the effects of common inorganic anions revealed that the presence of Clˉ and HCO₃ˉ exhibited different positive effects in the following order: Clˉ > HCO₃ˉ; NO₃ˉ and SO₄²ˉ showed inhibition effects on CT removal. The structure and properties of nZVI@SN‐rGO were characterized using X‐ray diffraction, scanning electron microscopy, surface area analysis, Raman spectroscopy and X‐ray photoelectron spectroscopy. Additionally, the corresponding activation energy was approximately 31.04 kJ mol^?1, suggesting that the surface chemical reaction rather than diffusion was the rate‐limiting step in the CT decomposition process. More importantly, the possible reaction mechanism and dechlorination pathway of CT using the ultrasound‐assisted nZVI@SN‐rGO system were also investigated.     

Synthesis of nanoscale zero‐valent iron modified graphene oxide nanosheets and its application for removing tetracycline antibiotic: Response surface methodology

Nowadays, pharmaceutical antibiotics are known as a serious class of pollutants. Therefore, it is important to develop effective methods for removing these pollutants from aqueous media. Different methods were applied for this purpose, and among these methods, chemical reduction by a cheap and eco‐friendly nanocatalyst is the most efficient and simplest method. In this research, based on graphene oxide supported by zero‐valent iron in mono‐, bi‐, and tri‐metallic systems, various nanocomposites were synthesized and used to degrade tetracycline as a model antibiotic from aqueous media. An investigation was carried out on the synergic effect among graphene oxide and the nano zero‐valent iron‐based tri‐metallic system as well as removal efficiencies. It was found that higher degradation efficiency is yielded by graphene oxide supported by Fe/Cu/Ag tri‐metallic system. The maximum synergic effect occurs at an acidic medium. The Brunauer–Emmett–Teller, Fourier transform spectroscopy, scanning electron microscopy‐energy dispersive X‐ray analysis, transmission electron microscopy, and X‐ray diffraction analysis were used to characterize the synthesized nanocomposites, which has successfully proved the loading of nanoscale Fe/Cu/Ag tri‐metallic on a graphene oxide support. The central composite design was used to model and optimize all involved variables affecting antibiotic removal efficiency. The consequences illustrated the optimum condition regarding the removal of 50 ppm of tetracycline, for the nanocomposites dose of 3.0 mg ml^?1, the contact time of 30 min, and pH of 2, was achieved using the simplex non‐linear optimization method. Moreover, antibiotic adsorption kinetic models were also investigated. Finally, the tetracycline removal from aqueous media at different concentrations, 25, 50, and 75 ppm, was successful by applying the proposed nanocomposite, and the results showed tetracycline removal efficiencies of above 70%.     

Supercritical Carbon Dioxide Assisted Deposition of Fe3O4 Nanoparticles on Hierarchical Porous Carbon and Their Lithium‐Storage Performance

A composite of highly dispersed Fe₃O₄ nanoparticles (NPs) anchored in three‐dimensional hierarchical porous carbon networks (Fe₃O₄/3DHPC) as an anode material for lithium‐ion batteries (LIBs) was prepared by means of a deposition technique assisted by a supercritical carbon dioxide (scCO₂)‐expanded ethanol solution. The as‐synthesized Fe₃O₄/3DHPC composite exhibits a bimodal porous 3D architecture with mutually connected 3.7 nm mesopores defined in the macroporous wall on which a layer of small and uniform Fe₃O₄ NPs was closely coated. As an anode material for LIBs, the Fe₃O₄/3DHPC composite with 79 wt % Fe₃O₄ (Fe₃O₄/3DHPC‐79) delivered a high reversible capacity of 1462 mA h g^?1 after 100 cycles at a current density of 100 mA g^?1, and maintained good high‐rate performance (728, 507, and 239 mA h g^?1 at 1, 2, and 5 C, respectively). Moreover, it showed excellent long‐term cycling performance at high current densities, 1 and 2 A g^?1. The enhanced lithium‐storage behavior can be attributed to the synergistic effect of the porous support and the homogeneous Fe₃O₄ NPs. More importantly, this straightforward, highly efficient, and green synthetic route will definitely enrich the methodologies for the fabrication of carbon‐based transition‐metal oxide composites, and provide great potential materials for additional applications in supercapacitors, sensors, and catalyses.     

l‐Proline‐functionalized Fe3O4 nanoparticles as a novel magnetic chiral catalyst for the direct asymmetric Mannich reaction

l ‐Proline has been successfully anchored on the surface of magnetic nanoparticles and characterized using powder X‐ray diffraction, scanning electron microscopy, vibrating sample magnetometry and Fourier transform infrared spectroscopy. These nanoparticles as a chiral catalyst have been employed to promote the direct asymmetric Mannich reaction. The corresponding products are obtained in high yields with high level of diastereoselectivity (up to 99:1 dr) in the presence of Fe₃O₄– l ‐proline. Also this heterogeneous catalyst can be recovered easily and reused many times without significant loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Constructing magnetic Fe3O4‐Au@CeO2 hybrid nanofibers for selective catalytic degradation of organic dyes

Au nanoparticles (Au NPs) play a vital role in heterogeneous catalytic reactions. However, pristine Au NPs usually suffer from poor selectivity and difficult recyclability. In this work, Fe₃O₄‐Au@CeO₂ hybrid nanofibers were prepared via a simple one‐pot redox reaction between HAuCl₄ and Ce (NO₃)₃ in the presence of Fe₃O₄ nanofibers. CeO₂ shell was uniformly coated on the surface of Fe₃O₄ nanofibers to form a unique core‐shell structure, while Au NPs were encapsulated inside the CeO₂ shell. The as‐prepared Fe₃O₄‐Au@CeO₂ hybrid nanofibers have been proved to be positively surface charged due to the formation of CeO₂ shell, enabling them to be good candidates for predominant selective catalytic activity towards the degradation of negatively charged organic dyes. In addition, the Fe₃O₄‐Au@CeO₂ hybrid nanofibers showed magnetic properties, offering them excellent recyclable usability. This work presents a facile and effective solution to prepare magnetic noble metal/metal oxide hybrid nanomaterials with unique chemical structure and surface characteristic for promising applications in heterogeneous catalysis.     

Ultrafast Preparation of Monodisperse Fe3O4 Nanoparticles by Microwave‐Assisted Thermal Decomposition

Thermal decomposition, as the main synthetic procedure for the synthesis of magnetic nanoparticles (NPs), is facing several problems, such as high reaction temperatures and time consumption. An improved a microwave‐assisted thermal decomposition procedure has been developed by which monodisperse Fe₃O₄ NPs could be rapidly produced at a low aging temperature with high yield (90.1 %). The as‐synthesized NPs show excellent inductive heating and MRI properties in vitro. In contrast, Fe₃O₄ NPs synthesized by classical thermal decomposition were obtained in very low yield (20.3 %) with an overall poor quality. It was found for the first time that, besides precursors and solvents, magnetic NPs themselves could be heated by microwave irradiation during the synthetic process. These findings were demonstrated by a series of microwave‐heating experiments, Raman spectroscopy and vector‐network analysis, indicating that the initially formed magnetic Fe₃O₄ particles were able to transform microwave energy into heat directly and, thus, contribute to the nanoparticle growth.     

Mixed phase Fe2O3/Mn3O4 magnetic nanocomposite for enhanced adsorption of methyl orange dye: Neural network modeling and response surface methodology optimization

In this research, a novel magnetic mesoporous adsorbent with mixed phase of Fe₂O₃/Mn₃O₄ nanocomposite was prepared by a facile precipitating method and characterized extensively. The prepared nanocomposite was used as adsorbent for toxic methyl orange (MO) dye removal from aqua matrix considering its high surface area (178.27 m²/g) with high saturation magnetization (23.07 emu/g). Maximum dye adsorption occurs at solution pH 2.0 and the electrostatic attraction between anionic form of MO dye molecules and the positively charged nanocomposite surface is the main driving force behind this adsorption. Response surface methodology (RSM) was used for optimizing the process variables and maximum MO removal of 97.67% is obtained at optimum experimental condition with contact time, adsorbent dose and initial MO dye concentration of 45 min, 0.87 g/l and 116 mg/l, respectively. Artificial neural network (ANN) model with optimum topology of 3–5–1 was developed for predicting the MO removal (%), which has shown higher predictive ability than RSM model. Maximum adsorption capacity of this nanocomposite was found to be 322.58 mg/g from Langmuir isotherm model. Kinetic studies reveal the applicability of second‐order kinetic model with contribution of intra‐particle diffusion in this process.     

Synthesis of magnetic,reactive, and thermoresponsive Fe3O4 nanoparticles via surface‐initiated RAFT copolymerization of N‐isopropylacrylamide and acrolein

A reversible addition‐fragmentation chain transfer (RAFT) agent was directly anchored onto Fe₃O₄ nanoparticles in a simple procedure using a ligand exchange reaction of S‐1‐dodecyl‐S′‐(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate with oleic acid initially present on the surface of pristine Fe₃O₄ nanoparticles. The RAFT agent‐functionalized Fe₃O₄ nanoparticles were then used for the surface‐initiated RAFT copolymerization of N‐isopropylacrylamide and acrolein to fabricate structurally well‐defined hybrid nanoparticles with reactive and thermoresponsive poly(N‐isopropylacrylamide‐co‐acrolein) shell and magnetic Fe₃O₄ core. Evidence of a well‐controlled surface‐initiated RAFT copolymerization was gained from a linear increase of number‐average molecular weight with overall monomer conversions and relatively narrow molecular weight distributions of the copolymers grown from the nanoparticles. The resulting novel magnetic, reactive, and thermoresponsive core‐shell nanoparticles exhibited temperature‐trigged magnetic separation behavior and high ability to immobilize model protein BSA. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 542–550, 2010     

Thiourea dioxide‐grafted γ‐Fe2O3/HAp magnetic nanoparticles: Efficient,green and reusable nanocatalyst for synthesis of pyranopyridine derivatives

A novel t hiourea dioxide‐functionalized hydroxyapatite‐encapsulated hybrid core‐shell γ‐Fe₂O₃@HAp‐TUD nanoparticles (MNPs) were prepared and characterized by FT‐IR, EDX, SEM, XRD, TGA and VSM analytical methods. The catalytic activity of these MNPs was evaluated through one‐pot three‐component reactions between various substituted aldehydes, malononitrile and 3‐cyano‐6‐hydroxy‐4‐methyl‐pyridin‐2(1H )‐one to afford the corresponding pyrano[2,3‐b]pyridines in high yields under mild and solvent‐free conditions. The catalyst can be easily recycled in a magnetic field and reused in five consecutive runs without significant decrease of its catalytic activity.     

Confined Nanospace Pyrolysis for the Fabrication of Coaxial Fe3O4@C Hollow Particles with a Penetrated Mesochannel as a Superior Anode for Li‐Ion Batteries

In this study, a method is developed to fabricate Fe₃O₄@C particles with a coaxial and penetrated hollow mesochannel based on the concept of “confined nanospace pyrolysis”. The synthesis involves the production of a polydopamine coating followed by a silica coating on a rod‐shaped β‐FeOOH nanoparticle, and subsequent treatment by using confined nanospace pyrolysis and silica removal procedures. Typical coaxial hollow Fe₃O₄@C possesses a rice‐grain morphology and mesoporous structure with a large specific surface area, as well as a continuous and flexible carbon shell. Electrochemical tests reveal that the hollow Fe₃O₄@C with an open‐ended nanostructure delivers a high specific capacity (ca. 864 mA h g^?1 at 1 A g^?1), excellent rate capability with a capacity of about 582 mA h g^?1 at 2 A g^?1, and a high Coulombic efficiency (>97 %). The excellent electrochemical performance benefits from the hollow cavity with an inner diameter of 18 nm and a flexible carbon shell that can accommodate the volume change of the Fe₃O₄ during the lithium insertion/extraction processes as well as the large specific surface area and open inner cavity to facilitate the rapid diffusion of lithium ions from electrolyte to active material. This fabrication strategy can be used to generate a hollow or porous metal oxide structure for high‐performance Li‐ion batteries.     

Decoration of Fe3O4 nanoparticles on the surface of poly(acrylic acid) functionalized multi‐walled carbon nanotubes by covalent bonding

Fe₃O₄ nanoparticles were indirectly implanted onto functionalized multi‐walled carbon nanotubes (MWCNTs) leading to a nanocomposite with stronger magnetic performance. Poly(acrylic acid) (PAA) oligomer was first reacted with hydroxyl‐functionalized MWCNTs (MWCNTs‐OH) forming PAA‐grafted MWCNTs (PAA‐g‐MWCNTs). Subsequently, Fe₃O₄ nanoparticles were attached onto the surface of PAA‐g‐MWCNTs through an amidation reaction between the amino groups on the surface of Fe₃O₄ nanoparticles and the carboxyl groups of PAA. Fourier transform infrared spectra confirmed that the Fe₃O₄ nanoparticles and PAA‐g‐MWCNTs were indeed chemically linked. The morphology of the nanocomposites was characterized using transmission electron microscope (TEM). The surface and bulk structure of the nanocomposites were examined using X‐ray diffraction, X‐ray photoelectron spectrometer (XPS), and thermogravimetric analysis (TGA). The magnetic performance was characterized by vibrating sample magnetometer (VSM) and the magnetic saturation value of the magnetic nanocomposites was 47 emu g^?1. The resulting products could be separated from deionized water under an external magnetic field within about 15 s. Finally, the magnetorheological (MR) performances of the synthesized magnetic nanocomposites and pure Fe₃O₄ nanoparticles were examined using a rotational rheometer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Palladium immobilized on amidoxime‐functionalized magnetic Fe3O4 nanoparticles: a highly stable and efficient magnetically recoverable nanocatalyst for sonogashira coupling reaction

We describe the synthesis of a novel Fe₃O₄/amidoxime (AO)/Pd nanocatalyst by grafting of AO groups on Fe₃O₄ nanoparticles and subsequent deposition of Pd nanoparticles. Prior to grafting of AO, the 2‐cyanoethyl‐functionalized Fe₃O₄ nanoparticles prepared through combining 2‐cyanoethyltriethoxysilane and Fe₃O₄ were treated with hydroxylamine. The AO‐grafted Fe₃O₄ nanoparticles were then used as a platform for the deposition of Pd nanoparticles. The catalyst was characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, scanning and transmission electron microscopies, vibrating sample magnetometry, wavelength‐ and energy‐dispersive X‐ray spectroscopies and inductively coupled plasma analysis. Fe₃O₄/AO/Pd is novel phosphine‐free recyclable heterogeneous catalyst for Sonogashira reactions. Interestingly, the novel catalyst could be recovered in a facile manner from the reaction mixture by applying an external magnet device and recycled seven times without any significant loss in activity. Copyright © 2015 John Wiley & Sons, Ltd.     

α‐Fe2O3 Polyhedral Nanoparticles Enclosed by Different Crystal Facets: Tunable Synthesis,Formation Mechanism Analysis,and Facets‐dependent n‐Butanol Sensing Properties

Three kinds of polyhedral α‐Fe₂O₃ nanoparticles enclosed by different facets including oblique parallel hexahedrons (op‐hexahedral NPs), cracked oblique parallel hexahedrons (cop‐hexahedral NPs), and octadecahedral nanoparticles (octadecahedral NPs), were successfully prepared by simply changing only one reaction parameter in the hydrothermal process. The structural and morphological of the products were systematically studied using various characterizations including X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), revealing that the three kinds of α‐Fe₂O₃ nanoparticles were enclosed by {104}, {110}/{104}, and {102}/{012}/{104} crystal planes, respectively. The exposed facets and shape of the nanocrystals were found to be affected by the adding amount of ethylene glycol in the solvent. The gas‐sensing properties and mechanism of the α‐Fe₂O₃ samples were studied and analyzed, which indicated that the sensitivity of the three samples followed the order of octadecahedral NPs > cop‐hexahedral NPs > op‐hexahedral NPs due to the combined effects of specific surface area and oxygen defects in the nanocrystals.     

Determination of trace amounts of aromatic amines after magnetic solid‐phase extraction using silver‐modified Fe3O4/graphene nanocomposite

In this work, a fast and simple magnetic dispersive solid phase extraction methodology was developed utilizing Ag@magnetite nanoparticles@graphene nanocomposite as an efficient magnetic nanosorbent for preconcentration and determine of five aromatic amines in water samples. The sorbent was characterized by diverse characterization techniques. After the extraction, high‐performance liquid chromatography with UV detection was utilized to analysis the aromatic amines. The effects of different factors on the extraction process were studied thoroughly via design of experiment and desirability function. Detection limits and linear dynamic ranges were obtained in the range of 0.10–0.20 and 0.3–300 μg/L, respectively. The relative standard deviations (n = 5) were in the range of 4.3–6.5%. Eventually, the method was employed for determination of target aromatic amines in various water samples.     

Graphene‐Fe3O4 as a magnetic solid‐phase extraction sorbent coupled to capillary electrophoresis for the determination of sulfonamides in milk

Graphene‐Fe₃O₄ nanoparticles were prepared using one‐step solvothermal method and characterized by X‐ray diffraction, FTIR spectroscopy, scanning electron microscopy, and vibrating sample magnetometry. The results demonstrated that Fe₃O₄ nanoparticles were homogeneously anchored on graphene nanosheets. The as‐synthesized graphene‐Fe₃O₄ nanoparticles were employed as sorbent for magnetic solid‐phase extraction of sulfonamides in milk prior to capillary electrophoresis analysis. The optimal capillary electrophoresis conditions were as follows: 60 mmol/L Na₂HPO₄ containing 2 mmol/L ethylenediaminetetraacetic acid disodium salt and 24% v/v methanol as running buffer, separation voltage of 14 kV, and detection wavelength of 270 nm. The parameters affecting extraction efficiency including desorption solution, the amount of graphene‐Fe₃O₄ nanoparticles, extraction time, and sample pH were investigated in detail. Under the optimal conditions, good linearity (5–200 μg/L) with correlation coefficients ≥0.9910 was obtained. The limits of detection were 0.89–2.31 μg/L. The relative standard deviations for intraday and interday analyses were 4.9–8.5 and 4.0–9.0%, respectively. The proposed method was successfully applied to the analysis of sulfonamides in milk samples with recoveries ranging from 62.7 to 104.8% and relative standard deviations less than 10.2%.     

Green synthesis of reduced graphene oxide/Fe3O4/Ag ternary nanohybrid and its application as magnetically recoverable catalyst in the reduction of 4‐nitrophenol

Materials having both magnetic and catalytic properties have shown great potential for practical applications. Here, a reduced graphene oxide/iron oxide/silver nanohybrid (rGO/Fe₃O₄/Ag NH) ternary material was prepared by green synthesis of Ag on pre‐synthesized rGO/Fe₃O₄. The as‐prepared rGO/Fe₃O₄/Ag NH was characterized using Fourier transform infrared spectroscopy, X‐ray diffractometry, Raman spectroscopy, vibrating sample magnetometry, transmission electron microscopy and energy‐dispersive X‐ray spectroscopy. rGO sheets were covered with Fe₃O₄ (8–16 nm) and Ag (18–40 nm) nanoparticles at high densities. The mass percentages were 13.47% (rGO), 62.52% (Fe₃O₄) and 24.01% (Ag). rGO/Fe₃O₄/Ag NH exhibited superparamagnetic behavior with high saturated magnetization (29 emu g⁻¹ at 12 kOe), and efficiently catalyzed the reduction of 4‐nitrophenol (4‐NP) with a rate constant of 0.37 min⁻¹, comparable to those of Ag‐based nanocatalysts. The half‐life of 4‐NP in the presence of rGO/Fe₃O₄/Ag NH was ca 1.86 min. rGO/Fe₃O₄/Ag NH could be magnetically collected and reused, and retained a high conversion efficiency of 94.4% after the fourth cycle. rGO/Fe₃O₄/Ag NH could potentially be used as a magnetically recoverable catalyst in the reduction of 4‐NP and environmental remediation.