Magnetically Separable Fe3O4 Nanoparticles-Decorated Reduced Graphene Oxide Nanocomposite for Catalytic Wet Hydrogen Peroxide Oxidation

Fe₃O₄ nanoparticles-decorated reduced graphene oxide magnetic nanocomposites (Fe₃O₄/rGO NCs) were prepared by a facile one-step strategy, and further used as heterogeneous Fenton-like catalysts for catalytic wet hydrogen peroxide oxidation (CWHPO) of methylene blue (MB) at 25 °C and atmospheric pressure. The effects of variables such as the Fe₃O₄/rGO with the mass ratio of rGO, initial pH, MB concentration and H₂O₂ dosage were investigated. The Fe₃O₄/rGO NCs with rGO mass ratio of 10.0 wt % showed the highest H₂O₂-activating ability, which was six-fold than that of pure Fe₃O₄ nanoparticles (NPs). The resulting catalysts demonstrated high catalytic activity in a broad operation pH range from 5 to 9, and still retained 90.5 % catalytic activity after reuse in five cycles. Taking advantage of the combined benefits of rGO and magnetic Fe₃O₄ NPs, these Fe₃O₄/rGO NCs were confirmed as an efficient heterogeneous Fenton-like catalyst for CWHPO to treat organic pollutants. And a reasonable catalytic mechanism of Fe₃O₄/rGO NCs was proposed to interpret the degradation process.     

Synthesis of ultrathin carbon dots-coated iron oxide nanocubes decorated with silver nanoparticles and their excellent catalytic properties

A facile ultrasonic method has been successfully developed for the fabrication of multifunctional Fe₃O₄@carbon dot/Ag (Fe₃O₄@C-dot/Ag) nanocubes (NCs), and the resulting materials are well characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), Vibrating sample magnetometer (VSM) and fluorescence measurements. The Ag nanoparticles (NPs) are uniform and well dispersed on the surface of Fe₃O₄@C-dot, while maintaining the shape and the size of the core-shell Fe₃O₄@C-dot NCs. In addition, its catalytic activities are evaluated by measuring the reduction of p-nitroaniline (p-NA) and crystal violet (CV), and the composite materials exhibit excellent catalytic activity towards reduction of p-NA and CV dye, which is superior to most reported catalysts. The good catalytic performance of Fe₃O₄@C-dot/Ag NCs may be attributed to the specific characteristics of its nanostructure and the synergistic effect on the delivery of electrons between Ag NPs and Fe₃O₄@C-dot NCs. Furthermore, the as-prepared catalysts also show good activity for the reduction of other nitrobenzene analogs. The effect of solvent and reducing agent was also studied on the catalytic activity of Fe₃O₄@C-dot/Ag NCs. Most importantly, the Fe₃O₄@C-dot/Ag catalyst shows excellent recycling stabilities, which can be potentially applied in the fields of catalysis and green chemistry.     

A comparative study on the selective hydrogenation of α,β unsaturated aldehyde and ketone to unsaturated alcohols on Au supported catalysts

The hydrogenation of trans,4-phenyl,3-buten,2-one (benzalacetone) and trans,3-phenyl, propenal (cinnamaldehyde) was carried out on Au supported on iron oxides catalysts. Commercial goethite (FeOOH), maghemite (γFe₂O₃) and hematite (αFe₂O₃) were used as supports. The catalytic activity of Au/Fe₂O₃ reference catalyst, supplied by the World Gold Council, was also investigated. Gold catalysts and the parent supports were characterized by BET, X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of ammonia (NH₃-TPD) and high resolution transmission electron microscopy (HRTEM).Among the catalysts investigated Au supported on FeOOH shows the highest activity and selectivity to UA in the hydrogenation of unsaturated carbonyl compounds whereas Au supported on αFe₂O₃ are the less active and selective catalysts.The catalytic activity and selectivity to unsaturated alcohols (UA) in the hydrogenation of benzalacetone and cinnamaldehyde are less influenced by the morphology of gold particles and are mainly influenced by the nature of the support.A correlation between the reducibility of the catalysts and the activity and selectivity to UA has been found. Increasing the reducibility of the catalysts both the activity and selectivity to UA increase. These results let us to argue that active and selective sites are formed by negative gold particles formed through the electron transfer from the reduced support to the metal.     

Ultrafine palladium nanoparticle-bonded to polyetheylenimine grafted reduced graphene oxide nanosheets: Highly active and recyclable catalyst for degradation of dyes and pigments

Much attention has been increasingly focused on the applications of noble metal nanoparticles (NPs) for the catalytic degradation of various dyes and pigments in industrial wastewater. We have demonstrated that Pd NPs/Fe₃O₄-PEI-RGO nanohybrids exhibit high catalytic activity and excellent durability in reductive degradation of MO, R6G, RB. Specific surface area was successfully prepared by simultaneous reduction of Pd(OAc)₂ chelating to PEI grafted graphene oxide nanosheets modified with Fe₃O₄. The as-prepared Pd NPs/Fe₃O₄-PEI-RGO nanohybrids were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, high-resolution TEM and energy dispersive X-ray spectroscopy, and UV-lambda 800 spectrophotometer, respectively. The catalytic activity of Pd NPs/Fe₃O₄-PEI-RGO nanohybrids to the degradation of MO, R6G, RB with NaBH4 was tracked by UV-visible spectroscopy. It was clearly demonstrated that Pd NPs/Fe₃O₄-PEI-RGO nanohybrids exhibited high catalytic activity toward the degradation of dyes and pigments, which could be relevant to the high surface areas of Pd NPs and synergistic effect on transfer of electrons between reduced graphene oxide (RGO), PEI and Pd NPs. Notably, Pd NPs/Fe₃O₄-PEI-RGO nanohybrids were easily separated and recycled thirteen times without obvious decrease in system. Convincingly, Pd NPs/Fe₃O₄-PEI-RGO nanohybrids would be a promising catalyst for treating industrial wastewater.     

Deposition of Gold Particles on Mesoporous Catalyst Supports by Sonochemical Method, and their Catalytic Performance for CO Oxidation

Supported gold catalysts on the mesoporous (MSP) metal oxides were prepared by a one-step, ultrasound-assisted reduction method, and characterized by XRD, HRTEM, EDX, BET, and XPS analysis. Their catalytic activities were examined in the oxidation of CO. Compared to the Au/Fe₂O₃(MSP) catalyst, the Au/TiO₂(MSP) and Au/Fe₂O₃-TiO₂(MSP) catalysts exhibited higher catalytic activity in the oxidation of CO at low temperatures. The high catalytic activity of Au/TiO₂(MSP) was attributed to the metallic state of the gold nanoparticles, their small size (2–2.5 nm), and their high dispersion on the catalyst support.     

Hydrogen production by partial oxidation of methanol over bimetallic Au–Ru/Fe2O3 catalysts

Hydrogen production by partial oxidation of methanol (POM) was investigated over Au–Ru/Fe₂O₃ catalyst, prepared by deposition–precipitation. The activity of Au–Ru/Fe₂O₃ catalyst was compared with bulk Fe₂O₃, Au/Fe₂O₃ and Ru/Fe₂O₃ catalysts. The reaction parameters, such as O₂/CH₃OH molar ratio, calcination temperature and reaction temperature were optimized. The catalysts were characterized by ICP, XRD, TEM and TPR analyses. The catalytic activity towards hydrogen formation is found to be higher over the bimetallic Au–Ru/Fe₂O₃ catalyst compared to the monometallic Au/Fe₂O₃ and Ru/Fe₂O₃ catalysts. Bulk Fe₂O₃ showed negligible activity towards hydrogen formation. The enhanced activity and stability of the bimetallic Au–Ru/Fe₂O₃ catalyst has been explained in terms of strong metal–metal and metal–support interactions. The catalytic activity was found to depend on the partial pressure of oxygen, which also plays an important role in determining the product distribution. The catalytic behavior at various calcination temperatures suggests that chemical state of the support and particle size of Au and Ru plays an important role. The optimum calcination temperature for hydrogen selectivity is 673 K. The catalytic performance at various reaction temperatures, between 433 and 553 K shows that complete consumption of oxygen is observed at 493 K. Methanol conversion increases with rise in temperature and attains 100% at 523 K; hydrogen selectivity also increases with rise in temperature and reaches 92% at 553 K. The overall reactions involved are suggested as consecutive methanol combustion, partial oxidation, steam reforming and decomposition. CO produced by methanol decomposition is subsequently transformed into CO₂ by the water gas shift and CO oxidation reactions.     

Enhanced photocatalytic degradation of tri-chlorophenol by Fe3O4@TiO2@Au photocatalyst under visible-light

Heterogeneous Fe₃O₄@TiO₂@Au core-shell microspheres, a facile and highly efficient catalyst have been fabricated by a simple surface modification. The fabrication process involved the coating of TiO₂ nanoshell onto the magnetic core using by sol-gel process, and then the anchoring of Au nanoparticles onto the surface of the Fe₃O₄@TiO₂ microspheres through the wet chemical reaction of 3-aminopropyltriethoxysilane (APTES). The as-synthesized Fe₃O₄@TiO₂ microspheres exhibited a narrow size distribution, with a typical size of 350 nm and shell thickness of 25 nm. The Fe₃O₄@TiO₂@Au microspheres can be easily collected by applying external magnetic field due to the magnetic property of core Fe₃O₄ particles. Compared to unmodified Fe₃O₄@TiO₂ microspheres, the Fe₃O₄@TiO₂@Au microspheres showed higher photocatalytic activity for 2, 4, 6-trichlorophenol (TCP). The photocatalytic efficiency of the Fe₃O₄@TiO₂ microspheres was 28% after 40 min irradiation while, the efficiency of Fe₃O₄@TiO₂@Au microspheres was 98% at the same condition.     

Hydroformylation of olefins by Au/Co3O4 catalysts

The hydroformylation of olefins over supported gold catalysts in an autoclave reactor under mild conditions (100–140 °C, 3–5 MPa) has been studied. Over Au/AC (activated carbon), Au/PVP (polyvinylpyrrolidone), Au/Al₂O₃, Au/TiO₂, Au/Fe₂O₃, Au/ZnO, Au/CeO₂ and Co₃O₄, 1-olefin mainly remained unchanged and the major products were isomerized olefins or hydrogenated paraffin. In contrast, Au nanoparticles deposited on Co₃O₄ led to remarkably high catalytic activities in hydroformylation reaction with selectivities above 85% to desired aldehydes. The hydroformylation of olefins proceeds preferentially at temperatures below 140 °C, above which the reactions of olefins gradually shifted to isomerization and then to hydrogenation. It appeared that the activity and selectivity of hydroformylation reaction strongly depend on the molecular structure of olefins, which could be ascribed to steric constraints as internal olefins are relatively inappropriate to form alkyl group and subsequent acyl group by insertion of CO. The Au/Co₃O₄ catalyst can be recycled by simple decantation with slight decrease in catalytic activity along with an increase in recycle times, which is a great advantage over homogeneous catalysts. The role of gold nanoparticles can be assumed to dissociate hydrogen molecule into atomic species which reduce Co₃O₄ to Co metal under mild reaction conditions.     

Preparation of high-magnetization Fe3O4–NH2–Pd (0) catalyst for Heck reaction

A magnetically separable Fe₃O₄–NH₂–Pd (0) catalyst was easily synthesized by immobilizing Pd nanoparticles on the surface of magnetic Fe₃O₄–NH₂ microspheres. It was found that the combination of Fe₃O₄ and triethylene tetramine (TETA) could give rise to structurally stable catalytic sites. Furthermore, the high-magnetization Fe₃O₄–NH₂–Pd(0) catalyst can be recovered by magnet and reused for six runs for Heck reaction without significant loss in catalytic activity.     

Ambient temperature CO oxidation over gold nanoparticles (14 nm) supported on Mg(OH)2 nanosheets

Au/Mg(OH)₂ catalysts with two different sizes (4 and 14 nm) of Au nanoparticles (NPs) have been prepared by depositing pre-fabricated Au NPs onto Mg(OH)₂ nanosheets (NSs). It was found that 14 nm Au NPs supported on Mg(OH)₂ exhibited unexpected activity for CO oxidation at ambient temperature that could be comparable with those of Au NPs of 4 nm. The Mg(OH)₂ support was suggested to be responsible for the observed catalytic activity of larger gold supported catalysts.     

Influence of modifying additives on the catalytic activity and stability of Au/Fe2O3–MO x catalysts for the WGS reaction

The activity and stability of Au/Fe₂O₃–MO_x catalysts (M = Zr, Mg, Ca, Ni, La, Cu, Zn, Al, Ba, Cr, Co, Ce, Mo, Bi, Ti, Mn) in water-gas shift reaction were investigated extensively. The WGS activity and stability of Au/Fe₂O₃ is improved significantly upon addition of ZrO₂ and to a lesser extend MgO, CaO, NiO, La₂O₃, Cr₂O₃, CuO. In contrast, Bi, Ti and Mn oxides seriously decrease the catalytic activity while additions of Zn, Al, Ba, Co, Ce and Mo oxides do not influence evidently the catalytic activity and its stability. Based on the characterization using the methods of BET-surface area and pore structure XRF, XRD, and H₂–TPR for some of as-prepared and spent samples, it could be concluded that the catalytic activity of gold catalysts supported on composite oxide of Fe₂O₃–MO_x depends not only on the dispersion of the gold particles but also on the reduction property of composite oxide supports, regardless of the fluctuation of gold loading and some change of specific surface area and pore structure due to introduction of the modifying metal oxides. The improvement of catalytic stability may be attributed to the comparative stabilization of high dispersion of gold particles and uneasily sintering of Fe₃O₄ crystallites during the catalytic operation. However, the chemical (electronic) effects exerted by the modifying addition of metal oxides on the catalytic performance of gold catalyst may not be ruled out.     

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.     

A novel method for the synthesis of Fe3O4 nanoparticles/CdS nanowires heterostructure nanocomposite and uses in photodegradation of methylene blue

We report here a simple, efficient, practical, and novel method for the preparation of Fe₃O₄ nanoparticles (NPs)/CdS nanowires. The CdS nanowire/Fe₃O₄ NP reported here was characterized by transmission electron microscopy (TEM), X-ray Diffraction (XRD), vibrating sample magnetometer (VSM), and energy-dispersive X-ray. Cadmium diethyl dithiophosphate has been used as a 3 in 1 precursor (cadmium, sulfur, and ligand source) for the synthesis of high-quality one-dimensional Fe₃O₄ NPs/CdS nanowires using a simple hydrothermal method in the presence of Fe₃O₄ NPs in water. Photocatalytic activity studies show that the nanocomposite has good photocatalytic activity toward the photodegradation of methylene blue in an aqueous solution.     

Fabrication of core-shell Fe3O4/polypyrrole and hollow polypyrrole microspheres

A facile synthesis of highly-regulated core-shell Fe₃O₄/polypyrrole (PPy) microspheres is achieved using a surfactant directed chemical oxidation polymerization in aqueous solution. The thickness of the PPy layer can be tuned by the quantity of the pyrrole monomer. The formation of core-shell Fe₃O₄/PPy microspheres lies on the static interactions between the SO₃⁻ group in sodium dodecyl sulphate molecules and Fe₃O₄ microspheres. Other surfactants such as cetyltrimethylammonium bromide and polyoxyethylene (10) isooctylcyclohexyl ether (Triton X-100) directed polymerization cannot produce such highly-regulated core-shell Fe₃O₄/PPy microspheres. XPS spectra proved the core-shell structure of the composite microspheres. XRD, FTIR, and UV–vis spectra are used to characterize the chemical structure of the composite microspheres. The electrical and magnetic properties are also investigated. Moreover, the obtained core-shell Fe₃O₄/PPy microspheres can be converted to highly-regulated hollow PPy microspheres by dissolving the Fe₃O₄ core with acid solution. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

An investigation of the activity of coprecipitated gold catalysts for methane oxidation

Coprecipitated Au on transition metal oxide catalysts have been tested for their activity toward methane oxidation. Catalyst activities fall in the order Au/Co₃O₄>Au/NiO> Au/MnO_x> Au/Fe₂O₃ > Au/CeO. The Au/Co₃O₄ catalyst is active just below about 250°C. The catalysts are proposed to have more than one type of reactive site since the supports are also active at higher temperatures. Analysis of spent catalysts with X-ray photoelectron spectroscopy indicates that Au exists in at least two oxidation states on some of them, a reduced state and an oxidized state. The activity for methane oxidation increases with increasing oxidation of Auin the oxidized state.     

Hydrothermal synthesis of 3D hollow porous Fe3O4 microspheres towards catalytic removal of organic pollutants

Three-dimensional hollow porous superparamagnetic Fe₃O₄ microspheres were synthesized via a facile hydrothermal process. A series of characterizations done with X-ray diffraction, Brunauer-Emmett-Teller method, Fourier transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy indicated that the production of Fe₃O₄ microspheres possessed good monodispersity, uniform size distribution, hollow and porous structural characters, and strong superparamagnetic behavior. The obtained Fe₃O₄ microspheres have a diameter of ca. 300 nm, which is composed of many interconnected nanoparticles with a size of ca. 20 nm. The saturation magnetization is 80.6 emu·g^-1. The as-prepared products had promising applications as novel catalysts to remove organic pollutants (methylene blue) from wastewater in the presence of H₂O₂ and ultrasound irradiation.     

Cellulose and chitosan based magnetic nanocomposite microspheres and its application

In this work, a simple and green method is used to fabricate magnet nanocomposite microspheres (cellulose/chitosan/Fe₃O₄) based on cellulose/chitosan microsphere via the interaction between metal ions with chitosan. The results of Fourier transform infrared spectra and X-ray diffraction indicated that the Fe₃O₄ nanoparticles were well-fixed in the network of cellulose/chitosan microsphere as a result of the chelation role between chitosan and metal ions. Moreover, the morphology of Fe₃O₄ nanoparticle can be adjusted by changing the chitosan concentration of cellulose/chitosan microsphere. Most important, the catalytic performance of the nanocomposite magnet microsphere was studied, and the magnet nanocomposite microspheres with face-centered cubic structure and less size of Fe₃O₄ nanoparticles have shown excellent catalytic performance. Based on their excellent catalytic properties, these magnet cellulose/chitosan/Fe₃O₄ microspheres have prospect applications in the field of biotechnology and environmental, and so on.     

CO oxidation at 20 °C over Au/SBA-15 catalysts decorated by Fe2O3 nanoparticles

This contribution describes the effect of SBA-15 substrate modification with variable amounts of Fe₂O₃ (5, 10, 15 and 20 wt.%) on the catalytic response of supported gold catalysts in CO oxidation at 20 °C. Catalytic activity was found to increase with the Fe₂O₃ loading even though this increase was not linear: the highest catalytic activity was observed for the catalyst loaded with 15 wt.% Fe₂O₃. For the most active Au/S15–15Fe catalyst, this behavior is explained in terms of the largest Fe₂O₃ cluster dispersion on the surface of the SBA-15 substrate (by XRD), the highest surface exposure of the Au⁰ species (by XPS) and its large stability during on-stream reaction.     

Morphology effects of Co3O4 on the catalytic activity of Au/Co3O4 catalysts for complete oxidation of trace ethylene

Au/Co₃O₄ catalysts with different morphologies (nanorods, nanopolyhedra and nanocubes) were successfully synthesized and evaluated for ethylene complete oxidation. We found that support morphology has a significant effect on catalytic activity, which is related to the exposed planes of different morphological Co₃O₄. HRTEM revealed the Co₃O₄-nanorods predominantly exposes {110} planes, while the dominant exposed planes of Co₃O₄-nanopolyhedra and -nanocubes are {011} and {001} planes, respectively. Compared with {011} and {001} planes, {110} planes exhibit the maximum amount of oxygen vacancies, which play a major role in ethylene oxidation. Therefore, Au/Co₃O₄-nanorods exhibits extraordinary catalytic activity, yielding 93.7% ethylene conversion at 0 °C.     

Preparation of stable magnetic nanofluids containing Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@PPy nanoparticles by a novel one-pot route

Stable magnetic nanofluids containing Fe₃O₄@Polypyrrole (PPy) nanoparticles (NPs) were prepared by using a facile and novel method, in which one-pot route was used. FeCl₃·6H₂O was applied as the iron source, and the oxidizing agent to produce PPy. Trisodium citrate (Na₃cit) was used as the reducing reagent to form Fe₃O₄ NPs. The as-prepared nanofluid can keep long-term stability. The Fe₃O₄@PPy NPs can still keep dispersing well after the nanofluid has been standing for 1 month and no sedimentation is found. The polymerization reaction of the pyrrole monomers took place with Fe³⁺ ions as the initiator, in which these Fe³⁺ ions remained in the solution adsorbed on the surface of the Fe₃O₄ NPs. Thus, the core-shell NPs of Fe₃O₄@PPy were obtained. The particle size of the as-prepared Fe₃O₄@PPy can be easily controlled from 7 to 30 nm by the polymerization reaction of the pyrrole monomers. The steric stabilization and weight of the NPs affect the stability of the nanofluids. The as-prepared Fe₃O₄@PPy NPs exhibit superparamagnetic behavior.