Novel Co_3O_4 Nanoparticles/Nitrogen-Doped Carbon Composites with Extraordinary Catalytic Activity for Oxygen Evolution Reaction(OER)

Herein, Co_3O_4 nanoparticles/nitrogen-doped carbon(Co_3O_4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precursors, which were then pyrolyzed in air to obtain Co_3O_4/NPC composites. When applied as catalysts for the oxygen evolution reaction(OER), the M-Co_3O_4/NPC composites derived from the flower-like ZIF-67 showedsuperior catalytic activities than those derived from the rhombic dodecahedron and hollow spherical ZIF-67. The former M-Co_3O_4/NPC composite displayed a small overpotential of 0.3 V, low onset potential of 1.41 V, small Tafel slope of 83 m V dec^(-1), and a desirable stability.(94.7% OER activity was retained after 10 h.) The excellent performance of the flower-like M-Co_3O_4/NPC composite in the OER was attributed to its favorable structure.

Synthesis and Characterization of Superparamagnetic Fe₃O₄@SiO₂Core-Shell Composite Nanoparticles

The Fe3O4@SiO2 composite nanoparticles were obtained from as-synthesized magnetite (Fe3O4) nanoparticles through the modified St?ber method. Then, the Fe3O4 nanoparticles and Fe3O4@SiO2 composite nanoparticles were characterized by means of X-ray diffraction (XRD), Raman spectra, scanning electron microscope (SEM) and vibrating sample magnetometer (VSM). Recently, the studies focus on how to improve the dispersion of composite particle and achieve good magnetic performance. Hence effects of the volume ratio of tetraethyl orthosilicate (TEOS) and magnetite colloid on the structural, morphological and magnetic properties of the composite nanoparticles were systematically investi-gated. The results revealed that the Fe3O4@SiO2 had better thermal stability and dispersion than the magnetite nanoparticles. Furthermore, the particle size and magnetic property of the Fe3O4@SiO2 composite nanoparticles can be adjusted by changing the volume ratio of TEOS and magnetite colloid.

Synthesis of Y_2O_3 particle enhanced Ni/TiC composite on TC4 Ti alloy by laser cladding

A Y2O3 particle enhanced Ni/TiC composite coating was fabricated in-situ on a TC4 Ti alloy by laser surface cladding. The phase component, microstructure, composition distribution and properties of the composite layer were investigated. The composite layer has graded microstructures and compositions, due to the fast melting followed by rapid solidification and cooling during laser cladding. The TiC powders are completely dissolved into the melted layer during melting and segregated as fine dendrites when solidified. The size of TiC dendrites decreases with increasing depth. Y2O3 fine particles distribute in the whole clad layer. The Y2O3 particle enhanced Ni/TiC composite layer has a quite uniform hardness along depth with a maximum value of HV1380, which is 4 times higher than the initial hardness. The wear resistance of the Ti alloy is significantly improved after laser cladding due to the high hardness of the composite coating.

Heterogeneous catalytic activation of peroxymonosulfate for efficient degradation of organic pollutants by magnetic Cu^0/Fe_3O_4 submicron composites

Magnetic Cu^0/Fe3O4 submicron composites were prepared using a hydrothermal method and used as heterogeneous catalysts for the activation of peroxymonosulfate（PMS） and the degradation of organic pollutants.The as-prepared magnetic Cu^0/Fe3O4 submicron composites were composed of Cu^0 and Fe3O4 crystals and had an average size of approximately 220 nm.The Cu^0/Fe3O4 composites could efficiently catalyze the activation of PMS to generate singlet oxygen,and thus induced the rapid degradation of rhodamine B,methylene blue,orange Ⅱ,phenol and 4-chlorophenol.The use of0.1 g/L of the Cu^0/Fe3O4 composites induced the complete removal of rhodamine B（20 μmol/L） in15 min,methylene blue（20 μmol/L） in 5 min,orange Ⅱ（20 μmol/L） in 10 min,phenol（0.1mmol/L） in 30 min and 4-chlorophenol（0.1 mmol/L） in 15 min with an initial pH value of 7.0 and a PMS concentration of 0.5 mmol/L.The total organic carbon（TOC） removal higher than 85%for all of these five pollutants was obtained in 30 min when the PMS concentration was 2.5 mmol/L.The rate of degradation was considerably higher than that obtained with Cu^0 or Fe3O4 particles alone.The enhanced catalytic activity of the Cu^0/Fe3O4 composites in the activation of PMS was attributed to the synergistic effect of the Cu^0 and Fe3O4 crystals in the composites.Singlet oxygen was identified as the primary reactive oxygen species responsible for pollutant degradation by electron spin resonance and radical quenching experiments.A possible mechanism for the activation of PMS by Cu^0/Fe3O4 composites is proposed as electron transfer from the organic pollutants to PMS induces the activation of PMS to generate ^1O2,which induces the degradation of the organic pollutants.As a magnetic catalyst,the Cu^0/Fe3O4 composites were easily recovered by magnetic separation,and exhibited excellent stability over five successive degradation cycles.The present study provides a facile and green heterogeneous catalysis method for the oxidative removal of organic pollutants.

Ultralow detection limit of giant magnetoresistance biosensor using Fe3O4–graphene composite nanoparticle label

A special Fe3O4nanoparticles–graphene（Fe3O4–GN） composite as a magnetic label was employed for biodetection using giant magnetoresistance（GMR） sensors with a Wheatstone bridge. The Fe3O4–GN composite exhibits a strong ferromagnetic behavior with the saturation magnetization MS of approximately 48 emu/g, coercivity HC of 200 Oe, and remanence Mr of 8.3 emu/g, leading to a large magnetic fringing field. However, the Fe3O4 nanoparticles do not aggregate together, which can be attributed to the pinning and separating effects of graphene sheet to the magnetic particles. The Fe3O4–GN composite is especially suitable for biodetection as a promising magnetic label since it combines two advantages of large fringing field and no aggregation. As a result, the concentration x dependence of voltage difference ｜？V｜ between detecting and reference sensors undergoes the relationship of ｜？V｜ = 240.5 lgx ＋ 515.2 with an ultralow detection limit of 10 ng/mL（very close to the calculated limit of 7 ng/mL） and a wide detection range of 4 orders.

Folate-conjugated Fe_3O_4 nanoparticles for in vivo tumor labeling

Highly biocompatible superparamagnetic Fe3O4 nanoparticles were synthesized by amide of folic acid （FA） ligands and the NH2-group onto the surface of Fe3O4 nanoparticles. The as-synthesized folate-conjugated Fe3O4 nanoparticles were characterized by X-ray diffraction diffractometer, transmission electron microscope, FT-IR spectrometer, vibrating sample magnetometer, and dynamic light scattering instrument. The in vivo labeling effect of folate-conjugated Fe3O4 nanoparticles on the hepatoma cells was investigated in tumor-bearing rat. The results demonstrate that the as-prepared nanoparticles have cubic structure of Fe3O4 with a particle size of about 8 nm and hydrated diameter of 25.7 nm at a saturation magnetization of 51 A·m2/kg. These nanoparticles possess good physiological stability, low cytotoxicity on human skin fibroblasts and negligible effect on Wistar rats at the concentration as high as 3 mg/kg body mass. The folate-conjugated Fe3O4 nanoparticles could be effectively mediated into the human hepatoma Bel 7402 cells through the binding of folate and folic acid receptor, enhancing the signal contrast of tumor tissue and surrounding normal tissue in MRI imaging. It is in favor of the tumor cells labeling, tracing, magnetic resonance imaging （MRI） target detection and magnetic hyperthermia.

Preparation and mechanical properties of in situ Al_2O_3/Al composites by adding NH_4AlO(OH)HCO_3

Aluminium matrix composite reinforced by Al2O3 particles was produced by adding NH4AlO（OH）HCO3 into molten aluminum.The mechanical properties and wear behavior of the as-fabricated composites were studied.The results show that during stirring γ-Al2O3 particles were formed via decomposition reaction of NH4AlO（OH）HCO3,and the distribution of Al2O3 particles is more uniform in the matrix aluminum than directly added Al2O3 into molten aluminum.The density and the hardness values of the as-fabricated composites increase with increasing the particle volume fraction,while the tensile strength of the composites decreases with increasing the volume fraction of the Al2O3 particles.The wear rate of the composites decreases with increasing the volume fraction of the particle and loading.The in situ formed Al2O3/Al composite by adding NH4AlO（OH）HCO3 shows more superior mechanical and wear behaviors than that prepared by directly adding Al2O3 particles.

Size-dependent peroxidase-like catalytic activity of Fe_3O_4 nanoparticles

Peroxidase-like catalytic properties of Fe3O4 nanoparficles （NPs） with three different sizes, synthesized by chemical coprecipitation and sol-gel methods, were investigated by UV-vis spectrum analysis. By comparing Fe3O4 NPs with average diameters of 11, 20, and 150 nm, we found that the catalytic activity increases with the reduced nanoparticle size. The electrochemical method to characterize the catalytic activity of Fe3O4 NPs using the response currents of the reaction product and substrate was also developed.

RhB Adsorption Performance of Magnetic Adsorbent Fe_3O_4/RGO Composite and Its Regeneration through A Fenton-like Reaction

Adsorption is one of the most effective technologies in the treatment of colored matter containing wastewater. Graphene related composites display potential to be an effective adsorbent. However, the adsorption mechanism and their regeneration approach are still demanding more efforts. An effective magnetically separable absorbent, Fe3O4 and reduced graphene oxide(RGO) composite has been prepared by an in situ coprecipitation and reduction method. According to the characterizations of TEM, XRD, XPS, Raman spectra and BET analyses, Fe3O4 nanoparticles in sizes of 10-20 nm are well dispersed over the RGO nanosheets, resulting in a highest specific area of 296.2 m2/g. The rhodamine B adsorption mechanism on the composites was investigated by the adsorption kinetics and isotherms. The isotherms are fitting better by Langmuir model, and the adsorption kinetic rates depend much on the chemical components of RGO. Compared to active carbon, the composite shows 3.7 times higher adsorption capacity and thirty times faster adsorption rates. Furthermore,with Fe3O4 nanoparticles as the in situ catalysts, the adsorption performance of composites can be restored by carrying out a Fenton-like reaction, which could be a promising regeneration way for the adsorbents in the organic pollutant removal of wastewater.

Preparation of Z-scheme WO_3(H_2O)_(0.333)/Ag_3PO_4 composites with enhanced photocatalytic activity and durability

Ag3PO4 is widely used in the field of photocatalysis because of its unique activity. However, photocorrosion limits its practical application. Therefore, it is very urgent to find a solution to improve the light corrosion resistance of Ag3PO4. Herein, the Z-scheme WO3(H2O)0.333/Ag3PO4 composites are successfully prepared through microwave hydrothermal and simple stirring. The WO3(H2O)0.333/Ag3PO4 composites are characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Vis spectroscopy. In the degradation of organic pollutants, WO3(H2O)0.333/Ag3PO4 composites exhibit excellent performance under visible light. This is mainly attributed to the synergy of WO3(H2O)0.333 and Ag3PO4. Especially, the photocatalytic activity of 15%WO3(H2O)0.333/Ag3PO4 is the highest, and the methylene blue can be completely degraded in 4 min. In addition, the stability of the composites is also greatly enhanced. After five cycles of testing, the photocatalytic activity of 15%WO3(H2O)0.333/Ag3PO4 is not obviously decreased. However, the degradation efficiency of Ag3PO4 was only 20.2%. This indicates that adding WO3(H2O)0.333 can significantly improve the photoetching resistance of Ag3PO4. Finally, Z-scheme photocatalytic mechanism is investigated.

Surface organic modification of Fe_3O_4 nanoparticles by silane-coupling agents

Fe3O4 nanoparticles were prepared by chemistry co-precipitation and the mean crystal size was 17.9 nm measured by XRD. After it had been treated by silane-coupling agents KH570, magnetic micro-spheres dispersed in organic medium glycol were gained and the mean size of Fe3O4 nanopowders was 33.7 nm. So it can be concluded that magnetic micro-sphere is made of a few Fe3O4 crystals. Many factors of modification were researched, such as the time of ball milling, the content of Fe3O4 and the content of KH570. The modification of Fe3O4 is relative to the time of ball milling, but the dominant function is affected by the content of Fe3O4 and KH570. When the content of Fe3O4 is known, there is a suitable content of KH570. Different content of Fe3O4 will make the different suitable content of KH570, but the range of latter is less than former, which is relative to the distribution of KH570 on Fe3O4 surface or in the solution.

Removing Cd^(2+) by Composite Adsorbent Nano-Fe_3O_4/Bacterial Cellulose

A new composite adsorbent, nano-Fe3O4/bacterial cellulose（BC）, was prepared through blending method. The process of adsorbing Cd2＋ including its isotherm and kinetics measured was studied. The results show that the adsorption efficiency is improved because of huge surface area and surface coordination of nano-Fe3O4 particles. Its adsorption capacity is 27.97 mg/g and the maximum of Cd2＋ removal is 74%. The adsorption kinetics can be described by pseudo-second rate model and the adsorption equilibrium by Langmuir type. The superparamagnetism of nano-Fe3O4 particles can help to solve the difficult separation of single BC adsorbent and lead to the quick separation of composite adsorbent from the liquid if a magnetic field was applied. Cd2＋ can be desorbed effectively by EDTA and HCl from the composite adsorbent, which can make it be reused.

Surface Organic Modification of Fe_3O_4 Magnetic Nanoparticles

The surface organic modification of Fe3O4 nanoparticles with silane coupling reagent KH570 was studied. The modified and unmodified nanoparticles were characterized by FT-IR, XPS and TEM. The spectra of FT-IR and XPS revealed that KH570 was coated onto the surface of Fe3O4 nanoparticles to get Fe-O- Si bond and an organic coating layer also was formed. Fe3O4 nanoparticles were spheres partly with mean size of 18,8 nm studied by TEM, which was consistent with the result 17.9 nm calculated by Scherrer＇s equation. KH570 was adsorbed on surface and formed chemistry bond to be steric hindrance repulsion which prevented nanoparticles from reuniting. Then glycol-based Fe3O4 magnetic liquids dispersed stably was gained.

Effect of Al2O3np on the Properties and Microstructure of B4Cp/Al Composites

Aluminum-matrix boron carbide (B4Cp/Al) is a kind of neutron absorbing material widely used in nuclear spent fuel storage. In order to improve the tensile property of B4Cp/Al composites, a new type of nano-Al2O3 particle (Al2O3np) reinforced B4Cp/Al + Al2O3np composites were prepared by powder metallurgy method. The Monte Carlo particle transport program (MCNP) was used to determine the influence of Al2O3np on the thermal neutron absorptivity of composites. The universal material testing machine and scanning electron microscope (SEM) were used to study the mechanical properties, microstructure and fracture morphology of B4Cp/Al composites. The results indicated that the neutron absorption properties of B4Cp/Al composites were not affected by the addition of nano-Al2O3 particles in the range of 1 wt%-15 wt%. The addition of Al2O3np can obviously reduce the grain size of B4Cp/Al matrix metals thus improve the tensile strength of the composites. The addition threshold of Al2O3np is about 2.5 wt%. Both B4Cp and Al2O3np change the fracture characteristics of the composites from toughness to brittleness, and the latter is more important.

Fe3O4 nanoparticles impregnated eggshell as a novel catalyst for enhanced biodiesel production

Biodiesel is a green fuel which can replace diesel while addressing various issues such as scarcity of hydrocarbon fuels and environmental pollution to an extent. The high production cost of biodiesel and the recovery of the catalyst after the transesterification process are the major challenges to be addressed in biodiesel production. In the present work, a cheap and promising solid base oxide catalyst was synthesized from chicken eggshell by calcination at 900 ℃ forming catalyst eggshells(CES) and was impregnated with the nanomagnetic material(Fe3O4) to obtain Fe3O4 loaded catalytic eggshell(CES–Fe3O4). Fe3O4 nanomaterials were synthesized by co-precipitation method and were loaded in catalytic eggshell by sonication, for better recovery of the catalyst after transesterification process. CES–Fe3O4 material was characterized by Thermogravimetric analysis, X-ray diffraction, Fourier transform infrared spectroscopy, a vibrating-sample magnetometer, Brunauer-Emmett-Teller, Dynamic light scattering, and Scanning electron microscopy. Biodiesel was synthesized by transesterification of Pongamia pinnata raw oil with 1:12 oil to methanol molar ratio and 2 wt% catalyst loading for 2 h at a temperature of 65 ℃ and yields were compared. The reusability of the catalyst was studied by the transesterification of the raw oil and its catalytic activity was found to be retained up to 7 cycles with a yield of 98%.

Intensification of levofloxacin sono-degradation in a US/H_2O_2 system with Fe_3O_4 magnetic nanoparticles

Fe3O4 magnetic nanoparticles(MNPs) were synthesised, characterised, and used as a peroxidase mimetic to accelerate levofloxacin sono-degradation in an ultrasound(US)/H2O2 system. The Fe3O4 MNPs were in nanometre scale with an average diameter of approximately 12 to 18 nm. The introduction of Fe3O4 MNPs increased levofloxacin sono-degradation in the US/H2O2 system. Experimental parameters, such as Fe3O4 MNP dose, initial solution p H, and H2O2 concentration, were investigated by a one-factor-at-a-time approach. The results showed that Fe3O4 MNPs enhanced levofloxacin removal in the p H range from 4.0 to 9.0. Levofloxacin removal ratio increased with Fe3O4 MNP dose up to 1.0 g·L-1and with H2O2 concentration until reaching the maximum. Moreover, three main intermediate compounds were identified by HPLC with electrospray ionisation tandem mass spectrometry, and a possible degradation pathway was proposed. This study suggests that combination of H2O2, Fe3O4 MNPs and US is a good way to improve the degradation efficiency of antibiotics.

Fabrication of Fine-Grained Si_3N_4-Si_2N_2O Composites by Sintering Amorphous Nano-sized Silicon Nitride Powders

Si3N4-Si2N2O composites were fabricated with amorphous nano-sized silicon nitride powders by the liquid phase sintering （ LPS ）. The Si2 N2O phase was generated by an in-situ reaction 2 Si3 N4 （ s ） ＋ 1.5 02 （ g ） = 3 Si2 N2O （ s ） ＋ N2 （ g ） . The content of Si2 N2 O phase up to 60% in the volume was obtained at a sintering temperature of 1 650℃ and reduced when the sintering temperature increased or decreased, indicating the reaction is reversible. The mass loss, relative density and average grain size increased with increasing the sintering temperature. The average grain size was less than 500 nm when the sintering temperature was below 1 700 ℃. The sintering procedure contains a complex crystallization and a phase transition ： amorphous silicon nitride→equiaxial α- Si3 N4→ equiaxial β- Si3 N4→ rod- like Si2 N2O→ needle- like β- Si3N4 . Small round-shaped β→ Si3 N4 particles were entrapped in the Si2 N2O grains and a high density of staking faults was situated in the middle of Si2 N2O grains at a sintering temperature of 1 650 ℃. The toughness inereased from 3.5 MPa·m^1/2 at 1 600 ℃ to 7.2 MPa· m^1/2 at 1 800 ℃ . The hardness was as high as 21.5 GPa （Vickers） at 1 600 ℃ .

Characteristics of magnetic Fe_3O_4 nanoparticles encapsulated with human serum albumin

Magnetic nanoparticles （Fe304） were prepared by chemical precipitation method using Fe^2＋ and Fe^3＋ salts with sodium hydroxide in the nitrogen atmosphere. Fe3O4 nanoparticles were coated with human serum albumin（HSA） for magnetic resonance imaging as contrast agent. Characteristics of magnetic particles coated or uncoated were carried out using scanning electron microscopy and X-ray diffraction. Zeta potentials, package effects and distributions of colloid particles were measured to confirm the attachment of HSA on magnetic particles. Effects of Fe3O4 nanoparticles coated with HSA on magnetic resonance imaging were investigated with rats. The experimental results show that the adsorption of HSA on magnetic particles is very favorable to dispersing of magnetic Fe3O4 particles, while the sizes of Fe3O4 particles coated are related to the molar ratio of Fe3O4 to HSA. The diameters of the majority of particles coated are less than 100 nm. Fe3O4 nanoparticle coated with HSA has a good biocompatibility and low toxicity. This new contrast agent has some effects on the nuclear magnetic resonance imaging of liver and the lowest dosage is 20μmol/kg for the demands of diagnosis.

Modification of Fe_3O_4 Magnetic Nanoparticles by L-dopa or Dopamine as an Enzyme Support

Fe3O4 magnetic nanoparticles were prepared by co-precipitation of Fe^2＋ and Fe^3＋ in an ammonia solution, and its size was about 36 nm measured by an atomic force microscope. Fe3O4 magnetic nanoparticles were modified by L-dopa or dopamine using sonication method. The analysis of FTIR clearly indicated the formation of Fe-O-C bond. Direct immobilization of trypsin （EC： 3.4.21.4） on Fe3O4 magnetic nanoparticles with L-dopa and dopamine spacer was investigated using glutaraldehyde as a coupling agent. No significant changes in the size and magnetic property of the three kinds of magnetic nanoparticles linked with or without trypsin were observed. The existence of the spacer molecule on magnetic nanoparticles could greatly improve the activity and the storage stability of bound trypsin through increasing the flexibility of enzyme and changing the microenvironment on nanoparticles surface compared to the naked magnetic nanoparticles.

Fe_3O_4 Magnetic Nanoparticles Modified Electrode as a Sensor for Determination of Nimesulide

A novel type of Fe3O4 nanoparticles modified glass carbon electrode（Fe3O4/GCE） was constructed and the electrochemical properties of N-（4-nitro-2-phenoxyphenyl）methanesulfonamide（nimesulide） were studied on the Fe3O4/GCE.In 0.4mol/L HAc-NaAc buffer solution（pH=5.0）,the electrode process of nimesulide was irreversible at bare GCE and Fe3O4/GCE.The Fe3O4/GCE exhibited a remarkable catalytic and enhancement effect on the reduction of nimesulide.The reduction peak potential of nimesulide shifted positively from-0.683 V at bare GCE to-0.625 V at Fe3O4/GCE,and the sensitivity was increased by ca.3 times.Some experimental conditions were optimized.The linear range between the peak current and the concentration of nimesulide was 2.6×10-6 ＂1.0×10-4mol/L（R=0.993） with a detection limit of 1.3×10-7mol/L.This method has been used to determine the content of nimesulide in medical tablets.The recovery was determined to be 96.9% ＂101.9% by means of standard addition method.The method is comparable to UV-Vis spectrometry.