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1.
The evolution under open-circuit conditions of iron passive films formed at 0.8 VSCE in a borate buffer solution at pH 8.4 was investigated with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. The composition of the freshly formed passive film as determined by X-ray photoelectron spectroscopy (XPS) was found to be in agreement with a bilayer model, where the inner layer is composed mainly of iron oxide and the outer layer consists of a hydrated material. Results of XPS measurements also showed that the open-circuit breakdown of passive films was consistent with a reductive dissolution mechanism. When the iron electrode reached an intermediate stage in the open-circuit potential decay (approximately −0.3 VSCE), the oxide film, containing both Fe(II) and Fe(III), was still protective. The impedance response in this stage exhibited a mixed control by charge transfer at the metal/film and film/solution interfaces and diffusion of point defects through the film. At the final stage of the open-circuit potential decay (approximately −0.7 VSCE), the oxide film was very thin, and the ratio of Fe3+/Fe2+ and O2−/OH had decreased significantly. The impedance response also exhibited a mixed charge-transfer–diffusion control, but the diffusion process was related to transport of species in the electrolyte solution resulting from dissolution of the oxide film.  相似文献   

2.
A poly(2,5-dimethoxyaniline) (PDMA) film was coated on the iron surface by the electropolymerization of 2,5-dimethoxyaniline in neutral buffer solution (pH?6.86). The PDMA film strongly adhered to the surface because of the polar methoxy groups of the PDMA molecules. The fact that no electrochemical response of the PDMA film-coated iron electrode to dissolved Fe2+ exhibited that the PDMA film was less permeable to dissolved species, acting as a diffusion barrier against agents causing corrosion such as H2O and O2. The PDMA film coating greatly lowered the anodic current peak ascribed to the anodic dissolution of iron and the corrosion current in strongly acidic medium, 0.5?M H2SO4 aqueous solution (1?M?????mol?dm??) as well as neutral medium (pH?6.86). The high anti-corrosion ability was due to a hybrid effect of the PDMA film not only as the diffusion barrier, but also as an in situ oxidant in spite of the slight redox activity of PDMA. In addition, the PDMA film is much more durable and adhesive than polyaniline film against over-oxidation.  相似文献   

3.
We report here the electrocatalytic reduction of oxygen on thin anthraquindisulfonate (AQDS)/poplypyrrole (PPy) composite film modified electrodes and its application to the electrooxidation of azo dye‐amaranth. The polymer‐coated cathode exhibited good electrocatalytic activity towards oxygen reduction reaction (ORR), and allowed the formation of strong oxidant hydroxyl radical (.OH) in the medium via Electro‐Fenton's reaction between cathodically generated H2O2 and added or regenerated Fe2+. The electrochemical behaviors of ORR in various pH solutions were described using cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometric (CA) techniques. The effect of solution pH on amaranth mineralization by the Fe2+/H2O2 and Fe3+/H2O2 electrooxidation systems was studied. In addition, the long‐term electrocatalytic activity and stability of the AQDS/PPy composite film during multiple experimental runs were also examined electrochemically.  相似文献   

4.
The large‐scale industrial production of acetic acid (HAc) from carbonylation of methanol has enabled intense research interest from direct hydrogenation of HAc to acetaldehyde (AA). Herein, a series of cerium‐iron oxide solid solution supported metallic cobalt catalysts were prepared by modified sol‐gel method and were applied in gas‐phase hydrogenation of HAc to AA. A synergistic effect between the hydrogenation metal cobalt and Ce‐Fe oxide solid solution is revealed. Specifically, oxygen vacancies provide the active sites for adsorption of HAc, while highly uniformly dispersed metallic Co adsorbs H2 and activates the reduction of HAc into AA. Moreover, the metallic Co can also assist the cyclical conversion between Fe3+/Fe2+ and Ce3+/Ce4+ on the surface of Ce1‐xFexO2‐δ supports. The unique effect substantially enhances the ability of the support material to rapidly capture oxygen atoms from HAc. It is found that the catalyst of 5% Co/Ce0.8Fe0.2O2‐δ with the highest concentration of oxygen vacancy presents the best catalytic performance (i.e. acetaldehyde yield reaches 49.9%) under the optimal reaction conditions (i.e. 623 K and H2 flow rate = 10 mL/min). This work indicates that the Co/Ce‐Fe oxide solid solution catalyst can be potentially used for the selective hydrogenation from HAc to AA. The synergy between the metallic Co and Ce1‐xFexO2‐δ revealed can be extended to the design of other composite catalysts.  相似文献   

5.
《中国化学快报》2020,31(10):2634-2640
It is generally recognized that the formation and accumulation of iron oxides on the surface of zero-valent iron (Fe0) resulting in significant decrease of contaminant degradation rates during the long-term reactions. However, in this study, we found that the removal efficiencies of p-nitrophenol (PNP) by micro zero-valent iron (mFe0) could maintain at the satisfactory level in the process of continuous reactions (20 cycles). The removal rate constant (0.1779 min−1) of the 5th cycle was 6.74 times higher than that of the 1st reaction (0.0264 min−1), even the 20th cycle (0.0371 min−1) was higher than that of the 1st reaction. Interestingly, almost no dissolved iron was detected in the solution, and the total iron concentrations decreased dramatically with the process of continuous reactions. The results of scanning electron microscope and energy dispersive spectrometry (SEM-EDS) and X-ray diffraction (XRD) revealed that the structure and composition of corrosion products change from amorphous to highly crystal with the increase of the number of cycles. The corrosion products were mainly magnetite (Fe3O4) and a small part of maghemite (γ-Fe2O3), which were in the form of microspheres on the surface of mFe0. The formation of surface oxidation shell hindered the release of Fe2+. X-ray photoelectron spectroscopy (XPS) results illustrated that partial Fe3O4 could be converted into γ-Fe2O3. Electrochemical analysis proved that the electron transfer rate of mFe0 increased with the formation of the oxides shell. However, the consumption of iron core and thicker oxide film weakened the electron transfer rate. Besides, the quenching experiments indicated that the reaction activity of mFe0 could be enhanced with the addition of scavengers. This study deepened the understanding of the structural transformation and radical production of mFe0 in continuous reactions.  相似文献   

6.
Electric properties and pitting susceptibility of passive films formed on iron in 0.01 M Na2CrO4 solution was investigated by using Mott–Schottky analyses, electrochemical noise analyses and anodic polarization curve measurements. It was found that the passive films were very disordered n-type semiconductors with two level donors, shallow and deep. The donor concentrations decreased as the passive film was formed at more positive potentials. The passive films were susceptible to pitting in the solution containing 0.05 M chloride ions. The pitting susceptibility of the passive film was improved as the donor concentration in the passive film decreased.  相似文献   

7.
A series of mixed oxides Ce1 ? x Fe x O2 was prepared by a hydrothermal method. XRD and Raman spectra were measured to study the structure of the prepared materials. The temperature-programmed reduction was undertaken to estimate reducibility of the oxides. Syngas generation from methane using these materials as oxygen carriers/catalysts via a chemical-looping procedure was investigated in detail. This procedure includes catalytic oxidation and decomposition of methane to produce H2-rich gas at the first step followed by the production of the CO-rich gas by oxidizing the carbon deposited on deactivated catalysts. The results showed that all iron ions were incorporated into the ceria lattice with the formation of oxygen vacancies in the Ce0.9Fe0.1O2 sample, while isolated Fe2O3 particles were distributed on the surface of the Ce0.8Fe0.2O2 sample. TPR measurements and the analysis of the two-step chemical-looping reactions indicated a strong interaction between the Ce and Fe species which accounts for an increased activity of the mixed oxides in the syngas generation compared to that of individual oxides. Among the several samples, the Ce0.8Fe0.2O2 catalyst showed the highest activity for methane partial oxidation due to the synergetic effects caused by the interaction of surface iron entities and Ce-Fe solid solution. In addition, selective oxidation of carbon by oxygen to CO can also be found over this material since gaseous products are formed at the carbon oxidation step with the selectivity to CO reaching 91.2%. Evidence is presented that syngas can be feasibly produced from methane with high selectivity via the chemical-looping procedure over the CeO2-Fe2O3 mixed oxides.  相似文献   

8.
Nano‐scale zero‐valent Iron (nZVI) attached on the Fe3O4 nanoparticles were prepared and creatively applied in the reductive dechlorination of Carbon Tetrachloride (CT). The characterization results of the synthesized composite indicated a main component of nZVI particles assembled on the surface of Fe3O4 with a layer of iron‐oxide film on the periphery, of which the dispersibility was better and the specific surface area was larger. The effects of different reaction conditions like temperature, initial pH values, Fe0@Fe3O4 dosage and initial CT concentrations on the removal of CT were evaluated. Under the optimum conditions, the Fe0@Fe3O4 composites showed a CT removal efficiency of 89.1% in 60 min, which was much greater than that of nZVI (61.7%) and Fe3O4 particles (14.3%). The removal process obeyed the pseudo‐first‐order kinetic model. Synergy effects of the constituents in the composite which can promote the relative rates of mass transfer to reactive sites were proposed to be existed and the magnetism of Fe3O4 could help to overcome the aggregation and surface passivation problem of nZVI. Thus, Fe0@Fe3O4 nanoparticles in our study can effectively complete the reductive dechlorination of CT and an improved nZVI catalyst is provided for the remediation of chlorinated organic compounds.  相似文献   

9.
We demonstrate the guiding principles behind simple two dimensional self‐assembly of MOF nanoparticles (NPs) and oleic acid capped iron oxide (Fe3O4) NCs into a uniform two‐dimensional bi‐layered superstructure. This self‐assembly process can be controlled by the energy of ligand–ligand interactions between surface ligands on Fe3O4 NCs and Zr6O4(OH)4(fumarate)6 MOF NPs. Scanning transmission electron microscopy (TEM)/energy‐dispersive X‐ray spectroscopy and TEM tomography confirm the hierarchical co‐assembly of Fe3O4 NCs with MOF NPs as ligand energies are manipulated to promote facile diffusion of the smaller NCs. First‐principles calculations and event‐driven molecular dynamics simulations indicate that the observed patterns are dictated by combination of ligand–surface and ligand–ligand interactions. This study opens a new avenue for design and self‐assembly of MOFs and NCs into high surface area assemblies, mimicking the structure of supported catalyst architectures, and provides a thorough fundamental understanding of the self‐assembly process, which could be a guide for designing functional materials with desired structure.  相似文献   

10.
To investigate whether a change in the valence state of tracer ions affects their diffusivity or not, the iron tracer diffusion in Al2O3-doped MgO, in which 0.5% of the cations were Al3+ ions, has been studied experimentally. Samples were prepared from high purity aluminum and magnesium nitrates using a chemical solution method and from powders of high purity Al2O3 and MgO. Because the concentration of the Al3+ dopant ions present in the samples was much larger than that of all other impurities, the concentration of the majority point defects, cation vacancies, was determined by the Al3+ concentration. Therefore, when changing the oxygen activity, the diffusivity of iron tracer ions can only be altered by changes in their valence state. Measurements of iron tracer diffusion coefficients were performed as a function of the oxygen activity at 1100 and 1200 °C. The experimental results indicate that the mean diffusivity of iron ions in Al2O3-doped MgO increases with increasing oxygen activity at both temperatures, suggesting that Fe3+ ions diffuse in Al2O3-doped MgO faster than Fe2+ ions.  相似文献   

11.
Bacitracin‐conjugated superparamagnetic iron oxide (Fe3O4) nanoparticles were prepared by click chemistry and their antibacterial activity was investigated. After functionalization with hydrophilic and biocompatible poly(acrylic acid), water‐soluble Fe3O4 nanoparticles were obtained. Propargylated Fe3O4 nanoparticles were then synthesized by carbodiimide reaction of propargylamine with the carboxyl groups on the surface of the iron oxide nanoparticles. By further reaction with N3‐bacitracin in a CuI‐catalyzed azide–alkyne cycloaddition, the magnetic Fe3O4 nanoparticles were modified with the peptide bacitracin. The functionalized magnetic nanoparticles were characterized by powder X‐ray diffraction, X‐ray photoelectron spectroscopy, TEM, zeta‐potential analysis, FTIR spectroscopy and vibrating‐sample magnetometry. Cell cytotoxicity tests indicate that bacitracin‐conjugated Fe3O4 nanoparticles show very low cytotoxicity to human fibroblast cells, even at relatively high concentrations. In view of the antibacterial activity of bacitracin, the biofunctionalized Fe3O4 nanoparticles exhibit an antibacterial effect against both Gram‐positive and Gram‐negative organisms, which is even higher than that of bacitracin itself. The enhanced antibacterial activity of the magnetic nanocomposites allows the dosage and the side effects of the antibiotic to be reduced. Due to the antibacterial effect and magnetism, the bacitracin‐functionalized magnetic nanoparticles have potential application in magnetic‐targeting biomedical applications.  相似文献   

12.
Direct electron transfer is demonstrated to occur between an electrode and hemoglobin that was immobilized on a film of Fe3O4@Pt-chitosan (Fe3O4@Pt-CS). Magnetic nanoparticles composed of Fe3O4 were prepared by a chemical coprecipitation method, and platinum nanoparticles were deposited on the Fe3O4 surface to form novel core-shell nanocomposites. In phosphate buffer solution of pH 7.0, the hemoglobin-Fe3O4@Pt-CS assembly on a modified glassy carbon electrode exhibited a couple of well-defined and quasi-reversible redox peaks. The formal potential E0′ was about ?0.35 V. The electrode displayed excellent electrocatalytic activity towards oxygen and hydrogen peroxide reduction without the need for an electron mediator.  相似文献   

13.
Metal–support interactions are frequently invoked to explain the enhanced catalytic activity of metal nanoparticles dispersed over reducible metal oxide supports, yet the atomic‐scale mechanisms are rarely known. In this report, scanning tunneling microscopy was used to study a Pt1‐6/Fe3O4 model catalyst exposed to CO, H2, O2, and mixtures thereof at 550 K. CO extracts lattice oxygen atoms at the cluster perimeter to form CO2, creating large holes in the metal oxide surface. H2 and O2 dissociate on the metal clusters and spill over onto the support. The former creates surface hydroxy groups, which react with the support, ultimately leading to the desorption of water, while oxygen atoms react with Fe from the bulk to create new Fe3O4(001) islands. The presence of the Pt is crucial because it catalyzes reactions that already occur on the bare iron oxide surface, but only at higher temperatures.  相似文献   

14.
In order to accelerate the reaction rate of water splitting, it is of immense importance to develop low‐cost, stable and efficient catalysts. In this study, the facile synthesis of a novel rose‐like nanocomposite catalyst (Ni2P/Fe2P/Fe3O4) is reported. The synthesis process includes a solvothermal step and a phosphatization step to combine iron oxides and iron‐nickel phosphides. Ni2P/Fe2P/Fe3O4 performs well in catalyzing oxygen evolution reaction, with a very low overpotential of 365 mV to reach 10 mA cm?2 current density. The Tafel slope is as low as 59 mV dec?1. Ni2P/Fe2P/Fe3O4 has a large double‐layer capacitance that contributes to a high electrochemically active area. Moreover, this catalyst is very stable for long‐term use. Therefore, the Ni2P/Fe2P/Fe3O4 catalyst has a high potential for use in oxygen evolution reactions.  相似文献   

15.
In this study, a novel multifunctional poly(arylene ether nitriles)(PEN)/carbon nanotubes/Fe3O4 nanocomposite with high tensile strength, magnetic, and electrical properties was investigated. First, we synthesized the monodisperse Fe3O4 nanoparticles on the surface of the multiwalled carbon nanotubes and then the hybrid material was compounded with PEN through the solution‐casting method. The SEM and TEM images indicated that the monodisperse Fe3O4 nanoparticles, with the diameters of 70∼80 nm, were self‐assembled along CNTs via the covalent bond method, which was confirmed by FTIR and XRD. The results of tensile properties showed that the tensile strength and modulus reached their highest values at the CNTs/Fe3O4 loading content of 1 wt % and both were greatly enhanced after heat treatment. Electrical conductivity of the polymer was dramatically enhanced at the low loading level of CNTs/Fe3O4; the electrical percolation of was in the range of 5∼8 wt % of CNTs/Fe3O4. The magnetic study showed that the saturation magnetization (Ms) of PEN/CNTs/Fe3O4 nanocomposites increased with the increase of CNTs/Fe3O4 loading content, and the coercive force (Hc) of the nanocomposite was independent of the CNTs/Fe3O4 content. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

16.
We present a facile strategy to prepare the molecularly imprinted polymers layer on the surface of Fe3O4 nanoparticles with core‐shell structure via sol–gel condensation for recognition and enrichment of triclosan. The Fe3O4 nanoparticles were first synthesized by a solvothermal method. Then, template triclosan was self‐assembled with the functional monomer 3‐aminopropyltriethoxysilane on the silica‐coated Fe3O4 nanoparticles in the presence of ethanol and water. Finally, the molecularly imprinted polymers were formed on the surface of silica‐coated Fe3O4 nanoparticles to obtain the product. The morphology, magnetic susceptibility, adsorption, and recognition property of magnetic molecularly imprinted polymers were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffractometry, vibrating sample magnetometry, and re‐binding experiments. The magnetic molecularly imprinted polymers showed binding sites with good accessibility, fast adsorption rate, and high adsorption capacity (218.34 μg/g) to triclosan. The selectivity of magnetic molecularly imprinted polymers was evaluated by the rebinding capability of triclosan and two other structural analogues (phenol and p‐chlorophenol) in a mixed solution and good selectivity with an imprinting factor of 2.46 was obtained. The application of triclosan removal in environmental samples was demonstrated.  相似文献   

17.
Many iron‐containing enzymes involve metal–oxygen oxidants to carry out O2‐dependent transformation reactions. However, the selective oxidation of C H and CC bonds by biomimetic complexes using O2 remains a major challenge in bioinspired catalysis. The reactivity of iron–oxygen oxidants generated from an FeII–benzilate complex of a facial N3 ligand were thus investigated. The complex reacted with O2 to form a nucleophilic oxidant, whereas an electrophilic oxidant, intercepted by external substrates, was generated in the presence of a Lewis acid. Based on the mechanistic studies, a nucleophilic FeII–hydroperoxo species is proposed to form from the benzilate complex, which undergoes heterolytic O O bond cleavage in the presence of a Lewis acid to generate an FeIV–oxo–hydroxo oxidant. The electrophilic iron–oxygen oxidant selectively oxidizes sulfides to sulfoxides, alkenes to cis‐diols, and it hydroxylates the C H bonds of alkanes, including that of cyclohexane.  相似文献   

18.
Many iron‐containing enzymes involve metal–oxygen oxidants to carry out O2‐dependent transformation reactions. However, the selective oxidation of C? H and C?C bonds by biomimetic complexes using O2 remains a major challenge in bioinspired catalysis. The reactivity of iron–oxygen oxidants generated from an FeII–benzilate complex of a facial N3 ligand were thus investigated. The complex reacted with O2 to form a nucleophilic oxidant, whereas an electrophilic oxidant, intercepted by external substrates, was generated in the presence of a Lewis acid. Based on the mechanistic studies, a nucleophilic FeII–hydroperoxo species is proposed to form from the benzilate complex, which undergoes heterolytic O? O bond cleavage in the presence of a Lewis acid to generate an FeIV–oxo–hydroxo oxidant. The electrophilic iron–oxygen oxidant selectively oxidizes sulfides to sulfoxides, alkenes to cis‐diols, and it hydroxylates the C? H bonds of alkanes, including that of cyclohexane.  相似文献   

19.
First, attapulgite‐Fe3O4 magnetic filler (ATP‐Fe3O4) was prepared by using a chemical precipitation method. Subsequently, graphite oxide (GO) was prepared through Hummer method, and then reduced GO (RGO) was prepared through GO reduced by chitosan (CS). Finally, a series of WPU‐RGO/ATP‐Fe3O4/CS composites were prepared by introduced RGO/ATP‐Fe3O4/CS to waterborne polyurethane. The structure and properties were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X‐ray diffraction (XRD), vibrating sample magnetometry (VSM), thermogravimetric analysis TGA, conductivity test, and tensile test. The experimental results indicated that thermal stability and tensile strength of nanocomposites were improved with the increase of the content of RGO/ATP‐Fe3O4/CS. Meanwhile, with the increase of the RGO/ATP‐Fe3O4/CS content, the electrical and magnetic properties of WPU‐RGO/ATP‐Fe3O4/CS composites were improved. When the content of RGO/ATP‐Fe3O4/CS was 8 wt%, the electrical conductivity and the saturation magnetic strength of WPU‐RGO/ATP‐Fe3O4/CS composites were 3.1 × 10?7 S·cm?1 and 1.38 emu/g, respectively. WPU‐RGO/ATP‐Fe3O4/CS composites have excellent electrical and magnetic properties.  相似文献   

20.
This study describes the preparation of a nanocomposites fabricated from monodispersed 4‐nm iron oxide (Fe3O4) coated on the surface of carboxylic acid containing multi‐walled carbon nanotube (c‐MWCNT) and polypyrrole (PPy) by in situ chemical oxidative polymerization. High‐resolution transmission electron microscopy images and X‐ray diffraction (XRD) data indicate that the resulting Fe3O4 nanoparticles synthesized using the thermal decomposition are close to spherical dots with a particle size about 4 ± 0.2 nm. The resulting nanoparticles were further mixed with c‐MWCNT in an aqueous solution containing with anionic surfactant sodium bis(2‐ethylhexyl) sulfosuccinate to form one‐dimensional Fe3O4 coated c‐MWCNT template for further preparation of nanocomposite. Structural and morphological analysis using field‐emission scanning electron microscopy, high‐resolution transmission electron microscopy, and XRD showed that the fabricated Fe3O4 coated c‐MWCNT/PPy nanocomposites are one‐dimensional core (Fe3O4 coated c‐MWCNT)‐shell (PPy) structures. The conductivities of these Fe3O4 coated c‐MWCNT/PPy nanocomposites are about four times higher than those of pure PPy matrix. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 727–733, 2008  相似文献   

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