Structural and Magnetic Analyses of Magnetic Nanoparticles Coated with Oleate Molecules

Physical and chemical properties of the magnetic nanoparticles coated with oleate have been investigated by means of transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Mossbauer spectroscopy, superconducting quantum interference device (SQUID) magnetometry, infrared spectra (IR) and the contact angle device. The results show that doped Al ions in Fe3O4 nanoparticles are located on the octahedral sites of the spinel structure. Oleate is coated on the magnetic nanoparticles with two layers by chemical absorbing, the outer layer can be washed away. The wetting of the surface of magnetic nanoparticles coated with monolayer has been changed from hydrophilicity to hydrophobicity, and the nanoparticles can be dispersed very well in some organic solutions.     

Effect of Fuel to Oxidant Molar Ratio on Structural and DC Electrical Conductivity of ZnO Nanoparticles Prepared by Simple Solution Combustion Method

ZnO nanoparticles of different sizes were prepared by varying the molar ratio of glycine and zinc nitrate hexahydrate as fuel and oxidizer （0.1, 0.8, 1.11, 1.3, 1.5, 1.7, 2.0） by simple solution combustion method. UV-Visible spectrophotometry studies show that, the band gap of the prepared ZnO nanoparticles increases with increasing fuel to oxidant （F/O） molar ratio up to 1.7 revealing the formation of ZnO nanoparticles. The decrease in band gap for the sample of F/O molar ratio 2.0 is due to an increase in particle size. Powder X-ray diffraction patterns of the prepared samples show the formation of single phase ZnO nanoparticles and the particle size decreases with increasing F/O molar ratio up to 1.7. Surface morphology of the prepared samples was studied by scanning electron microscopy and it was observed that, the porosity increases with increasing F/O molar ratio. DC electrical conductivity at room temperature and in the temperature range of 303-563 K was studied for all the samples and the results revealed that, the sample of F/O molar ratio 1.7 has low electrical conductivity at room temperature and high EAR （high temperature activation energy） compared to other samples.     

Co^3＋—modified Surface of LiMn2O4 Spinel for its Improvementof Electrochemical Properties

Cobalt was used to modify the surface of spinel LiMn2O4 by a solution technique to produce Co^3 -modified surface material (COMSM). Cobalt was only doped into the surface of LiMn2O4 spinel. XPS(X-ray photoelectron spectroscopy) analysis confirms the valence state of Co^3 . COMSM has stable spinel structure and can prevent active materials from the corrosion of electrolyte. The ICP(inductively coupled plasma) determination of the spinel dissolution in electrolyte showed the content of Mn dissolved from COMSM was smaller than that from the pure spinel. AC impedance patterns show that the charge-transfer resistance (Rct) for COMSM is smaller than that for pure spinel. The particles of COMSM are bigger in size than those of pure spinel according to the micrographs of SEM(scanning electron microscopy). The determinations of the electrochemical characterization show that COMSM has both good cycling performance and high initial capacity of 124.1 mA/h at an average capacity loss of 0.19 mAh/g per cycle.     

Enhanced Cryogenic Magnetocaloric Effect Induced by Small Size GdNis Nanoparticles

GdNi5 nanoparticles and GdNis/Gd2O3 nanocapsules （with GdNi5 core and Gd2O3 shell） were prepared by arcdischarge technique under different hydrogen partial pressure. The GdNi5 nanoparticles show irregular spherical shape and have a size distribution of 10-50 nm with an average diameter of 15 nm. In comparison, the GdNi5/Gd2O3 nanocapsules present spherical morphology and show a size distribution of 10-100 nm with an average diameter of 60 nm. Under a magnetic field change of 50 kOe, the maximum magnetic entropy change of GdNi5 nanoparticles is 13.5 J/（kg K） at 5 K, while the corresponding value of the GdNis/Gd2O3 nanocapsuels is only 5.7 J/（kg K） at 31 K. The origin of the large magnetic entropy change of GdNi5 nanoparticles is ascribed to its high atomic moments and small anisotropy energy barrier induced by its small particle size.     

Catalase-imprinted Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Fe@fibrous SiO<Subscript>2</Subscript>/polydopamine nanoparticles: An integrated nanoplatform of magnetic targeting,magnetic resonance imaging,and dual-mode cancer therapy

Recent advances in the research on the molecular mechanism of cell death and methods for preparation of nanomaterials make the integration of various therapeutic approaches,targeting,and imaging modes into a single nanoscale complex a new trend for the development of future nanotherapeutics.Hence,a novel ellipsoidal composite nanoplatform composed of a magnetic Fe3O4/Fe nanorod core (～120 nm) enwrapped by a catalase (CAT)-imprinted fibrous SiO2/ polydopamine (F-SiO2/PDA) shell with thickness 70 nm was prepared in this work.In vitro experiments showed that the Fe3O4/Fe@F-SiO2/PDA nanoparticles can selectively inhibit the bioactivity of CAT in tumor cells by the molecular imprinting technique.As a result,the H2O2 level in tumor cells was elevated dramatically.At the same time,the Fe3O4/Fe core released Fe ions to catalyze the conversion of H2O2 to ·OH in tumor cells.Eventually,the concentration of ·OH in tumor cells rapidly rose to a lethal level thus triggering apoptosis.Combined with the remarkable near-infrared light (NIR) photothermal effect of the CATimprinted PDA layer,the Fe3O4/Fe@F-SiO2/PDA nanoparticles can effectively kill MCF-7,HeLa,and 293T tumor cells but are not toxic to nontumor cells.Furthermore,these nanoparticles show good capacity for magnetic targeting and suitability for magnetic resonance imaging (MRI).Therefore,the integrated multifunctional nanoplatform opens up new possibilities for high-efficiency visual targeted nonchemo therapy for cancer.     

Highly efficient multi-metal catalysts for carbon dioxide reduction prepared from atomically sequenced metal organic frameworks

The precise control on the combination of multiple metal atoms in the structure of metal-organic frameworks(MOFs)endowed by reticular chemistry,allows the obtaining of materials with compositions that are programmed for achieving enhanced reactivity.The present work illustrates how through the transformation of MOFs with desired arrangements of metal cations,multi-metal spinel oxides with precise compositions can be obtained,and used as catalyst precursor for the reverse water-gas shift reaction.The differences in the spinel initial composition and structure,determined by neutron powder diffraction,influence the overall catalytic activity with changes in the process of in s itu formation of active,metal-oxide supported metal nanoparticles,which have been monitored and characterized with in situ X-ray diffraction and photoelectron spectroscopy studies.     

Synthesis and Characterization of NiFe2O4 Magnetic Nanoparticles by Combustion Method

Magnetic nanoparticles of nickel ferrite (NiFe2O4 ) have been successfully synthesized by microwave-assisted combustion method using stable ferric and nickel salts as precursors and glycine as fuel. The as-synthesized samples were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM) and field emission scanning electron microscopy (FESEM). The effect of different dose of glycine on the structural parameters and magnetic properties of the prepared NiFe2O4 nanoparticles was also investigated. This study revealed that it was possible to produce larger size of nanoparticles with lower saturation magnetization by using higher dose of fuel.     

Surface-Engineered Li4Ti5O12 Nanostructures for High-Power Li-Ion Batteries

Materials with high-power charge–discharge capabilities are of interest to overcome the power limitations of conventional Li-ion batteries.In this study,a unique solvothermal synthesis of Li4Ti5O12 nanoparticles is proposed by using an off-stoichiometric precursor ratio.A Li-deficient off-stoichiometry leads to the coexistence of phaseseparated crystalline nanoparticles of Li4Ti5O12 and TiO2 exhibiting reasonable high-rate performances.However,after the solvothermal process,an extended aging of the hydrolyzed solution leads to the formation of a Li4Ti5O12 nanoplate-like structure with a self-assembled disordered surface layer without crystalline TiO2.The Li4Ti5O12 nanoplates with the disordered surface layer deliver ultrahighrate performances for both charging and discharging in the range of 50–300C and reversible capacities of 156 and 113 mAh g−1 at these two rates,respectively.Furthermore,the electrode exhibits an ultrahigh-charging-rate capability up to 1200C(60 mAh g−1;discharge limited to 100C).Unlike previously reported high-rate half cells,we demonstrate a high-power Li-ion battery by coupling Li4Ti5O12 with a high-rate LiMn2O4 cathode.The full cell exhibits ultrafast charging/discharging for 140 and 12 s while retaining 97 and 66% of the anode theoretical capacity,respectively.Room-(25℃),low-(−10℃),and high-(55℃)temperature cycling data show the wide temperature operation range of the cell at a high rate of 100C.     

Silica shell-assisted synthetic route for mono-disperse persistent nanophosphors with enhanced in vivo recharged near-infrared persistent luminescence

Near-infrared (NIR) persistent-luminescence nanoparticles have emerged as a new class of background-free contrast agents that are promising for in vivo imaging.The next key roadblock is to establish a robust and controllable method for synthesizing monodisperse nanoparticles with high luminescence brightness and long persistent duration.Herein,we report a synthesis strategy involving the coating/etching of the SiO2 shell to obtain a new class of small NIR highly persistent luminescent ZnGa2O4∶Cr3+,Sn4+ (ZGOCS) nanoparticles.The optimized ZGOCS nanoparticles have an excellent size distribution of ～15 nm without any agglomeration and an NIR persistent luminescence that is enhanced by a factor of 13.5,owing to the key role of the SiO2 shell in preventing nanoparticle agglomeration after annealing.The ZGOCS nanoparticles have a signal-to-noise ratio ～3 times higher than that of previously reported ZnGa2O4∶Cr3+ (ZGC-1) nanoparticles as an NIR persistent-luminescence probe for in vivo bioimaging.Moreover,the persistent-luminescence signal from the ZGOCS nanoparticles can be repeatedly re-charged in situ with external excitation by a white lightemitting diode;thus,the nanoparticles are suitable for long-term in vivo imaging applications.Our study suggests an improved strategy for fabricating novel high-performance optical nanoparticles with good biocompatibility.     

A multifunctional nanoparticle system combines sonodynamic therapy and chemotherapy to treat hepatocellular carcinoma

Hepatocellular carcinoma (HCC) is one of the most common and deadly malignancies worldwide.To date,the survival of patients with HCC has not improved because of the insensitivity of HCC to conventional treatments.Sonodynamic therapy (SDT) is a promising new approach that shows remarkable potential in the treatment of HCC.Here,we designed a simple,biocompatible,and multifunctional nanosystem that combines SDT and chemotherapy to treat HCC.This nanosystem,called HPDF nanoparticles,had a core-shell structure in which hematoporphyrin (HP) was complexed with doxorubicin (DOX) to form the hydrophobic core and the surface was coated with Pluronic F68 to form the hydrophilic shell.In HCC cells,HPDF nanoparticles in combination with ultrasonic irradiation (1.0 MHz,1.5 W/cm2,30 s) exhibited potent cytotoxicity,resulting from the synergistic effects of a large amount of reactive oxygen species generated from HP and DOX-induced DNA damage.Notably,HPDF nanoparticles in combination with ultrasonic irradiation significantly reversed drug resistance in Nanog-positive cancer stem cells (CSCs) in HCC.In nude mice bearing HCC tumors,HPDF nanoparticles efficiently accumulated in the tumors and reached the maximum levels within 6-8 h,post intravenous injection.HPDF nanoparticles,in combination with ultrasonic irradiation (1.0 MHz,3 W/cm2,5 min),suppressed tumor growth,angiogenesis,and collagen deposition,considerably.In summary,our results show that HPDF nanoparticles can effectively combine SDT and chemotherapy to inhibit HCC growth and progression through multiple mechanisms in both cellular and animal models.     

锰锌铁氧体的低温合成及表征

采用溶胶-凝胶自燃烧法在低温下一步合成了纯相尖晶石结构的锰锌铁氧体(Mn0.5Zn0.5Fe2O4)纳米颗粒。其结构、形貌和热分解过程分别采用X射线衍射仪(XRD)、扫描电镜(SEM)和TG-DSC分析仪进行了表征。结果表明:在pH=7.0、柠檬酸与金属离子摩尔比为1∶1和柠檬酸的浓度为0.7mol/L的条件下,金属的硝酸盐和柠檬酸形成的干凝胶可通过自燃烧过程一步合成出平均粒径约为60nm的纯相Mn0.5Zn0.5Fe2O4铁氧体纳米颗粒。经过400℃煅烧后,颗粒粒径增大,衍射峰变窄,强度增加,晶型更趋于完整。     

微波多元醇法制备单分散Ni1-xZnxFe2O4/MWCNTs与磁性能

以多壁碳纳米管(MWCNTs)为模板,三乙二醇(TREG)为溶剂,采用微波多元醇法制备MWC-NTs负载组成可控的Ni1-xZnxFe2O4(x=0.4、0.5、0.6)纳米复合材料Ni1-xZnxFe2O4/MWCNTs。其结构和形貌通过XRD、SEM、TEM和EDX进行表征,用VSM测试样品的磁性,并探讨了微波功率、微波时间对镍锌铁氧体负载的影响。结果表明立方系尖晶石结构的单分散Ni1-xZnxFe2O4磁性纳米粒子均匀负载在碳纳米管表面,平均粒径约为6nm;其磁性能与镍锌铁氧体的组成有关,随着Zn含量的增加,饱和磁化强度(Ms)先增大后减小,当x=0.5时Ms达到最大值。矫顽力(Hc)都比较小,在室温下表现为超顺磁性。     

纳米MgO和MgAl2O4尖晶石的制备与表征

本文较详细地介绍了用无机盐Ａｌ（ＮＯ３）３９Ｈ２Ｏ和Ｍｇ（ＮＯ３）２．６Ｈ２Ｏ为原料，醇凝胶分段程序升温超临界流体干燥法，制备纳米ＭｇＯ和ＭｇＡｌ２Ｏ４尖晶石新型功能材料的方法，并对所制得的纳米粒子采用ＴＥＭ、ＸＲＤ和ＦＴ－Ｒ等现代分析测试手段进行了表面形貌、结构、晶型和组成等的表征，掌握了纳米粒子的一些特征。     

Microwave assisted semi-solvothermal synthesis of nanocrystalline barium titanate

In an endeavor to synthesize tetragonal nanocrystallites of BaTiO3 at much reduced reaction time, we explored the possibility of performing microwave assisted semi-solvothermal reaction by using Ba(OH)2 . 8H2O and amorphous titanium hydrous gel as precursors and 1,4-butanediol and water as solvent. Typically, such a microwave assisted reaction was accomplished within 2 hrs at 220 degrees C as against 12 hrs required in conventional approach. The crystallized BaTiO3 powders (microwave assisted as well as conventionally processed for reference) were characterized by X-ray diffraction, thermal analysis, infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. We have detected metastable cubic phase by XRD while locally symmetric tetragonal phase by Raman spectroscopy in case of conventional semi-solvothermal processing. On the contrary, we could detect co-existence of tetragonal and cubic phases by XRD and only tetragonal phase by Raman spectroscopy in case of microwave assisted semi-solvothermal processing. The TEM analysis indicates typical particle size distribution in the range of approximately 20 to 80 nm for conventionally processed powder while that in the range of approximately 20 to 50 nm for microwave processed powder. HRTEM images evince the distortion from an ideal cubic structure in case of microwave processed powder which can be correlated with anisotropic lattice contraction during the microwave induced heating. AFM analysis exhibited relatively less aggregation of nanoparticles for microwave assisted process.     

交联P（St-r-AA）包覆Fe3O4粒子的制备及对Cu2＋的吸附

用乳液聚合的方法合成了交联P（St-r-AA）包覆的Fe3O4粒子,研究了该类粒子对Cu2＋离子的吸附性能。透射电镜（TEM）表明,交联的P（St-r-AA）包覆的Fe3O4磁性粒子粒径约100 nm;X射线衍射（XRD）分析表明,磁性粒子中磁性物质为尖晶石结构的Fe3O4;红外光谱（FT-IR）表明,Fe3O4表面的...     

Microwave irradiation assisted rapid synthesis of Fe-Ru bimetallic nanoparticles and their catalytic properties in water-gas shift reaction

Fe-Ru bimetallic nanoparticles were prepared by a microwave irradiation assisted glycol reduction method using poly-N-vinyl-2-pyrrolidone (PVP) as protective agent. The structure and morphology of the nanoparticles were characterized by X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDXA) and high-resolution transmission electron microscopy (HRTEM). EDXA and XRD analysis confirmed the presence of Fe and Ru. The bimetallic nanoparticles were subsequently loaded onto an MgAl₂O₄ supporter with K₂O as promoters and used as catalyst for water-gas shift reaction. The results indicated that the FeRu bimetallic nanoparticles exhibit high catalytic activity for water-gas shift reaction due to the synergistic effect between iron and ruthenium. Potassium oxide can enhance the CO selectivity of the catalyst significantly besides increasing the catalyst activity.     

Catalytic activity of CuOn-La2O3/gamma-Al2O3 for microwave assisted ClO2 catalytic oxidation of phenol wastewater

In order to develop a catalyst with high activity and stability for microwave assisted ClO2 catalytic oxidation, we prepared CuOn-La2O3/gamma-Al2O3 by impregnation-deposition method, and determined its properties using BET, XRF, XPS and chemical analysis techniques. The test results show that, better thermal ability of gamma-Al2O3 and high loading of Cu in the catalyst can be achieved by adding La2O3. The microwave assisted ClO2 catalytic oxidation process with CuOn-La2O3/gamma-Al2O3 used as catalyst was also investigated, and the results show that the catalyst has an excellent catalytic activity in treating synthetic wastewater containing 100 mg/L phenol, and 91.66% of phenol and 50.35% of total organic carbon (TOC) can be removed under the optimum process conditions. Compared with no catalyst process, CuOn-La2O3/gamma-Al2O3 can effectively degrade contaminants in short reaction time and with low oxidant dosage, extensive pH range. The comparison of phenol removal efficiency in the different process indicates that microwave irradiation and catalyst work together to oxidize phenol effectively. It can therefore be concluded from results and discussion that CuOn-La2O3/gamma-Al2O3 is a suitable catalyst in microwave assisted ClO2 catalytic oxidation process.     

Ni doped Fe3O4 magnetic nanoparticles

In this work, the effect of nickel doping on the structural and magnetic properties of Fe3O4 nanoparticles is analysed. Ni(x)Fe(3-x)O4 nanoparticles (x = 0, 0.04, 0.06 and 0.11) were obtained by chemical co-precipitation method, starting from a mixture of FeCl2 x 4H2O and Ni(AcO)2 x 4H2O salts. The analysis of the structure and composition of the synthesized nanoparticles confirms their nanometer size (main sizes around 10 nm) and the inclusion of the Ni atoms in the characteristic spinel structure of the magnetite Fe3O4 phase. In order to characterize in detail the structure of the samples, X-ray absorption (XANES) measurements were performed on the Ni and Fe K-edges. The results indicate the oxidation of the Ni atoms to the 2+ state and the location of the Ni2+ cations in the Fe2+ octahedral sites. With respect to the magnetic properties, the samples display the characteristic superparamagnetic behaviour, with anhysteretic magnetic response at room temperature. The estimated magnetic moment confirms the partial substitution of the Fe2+ cations by Ni2+ atoms in the octahedral sites of the spinel structure.     

Facile microwave-combustion synthesis of wurtzite CdS nanoparticles

In this study we first report microwave-combustion synthesis of faceted CdS nanoparticles by using cadmium thiocyanate complex as a single source precursor. This is the first example of a metal-thiocyanate (M-SCN) complex being used as a source for metal sulfides (M-S) preparation in a microwave-combustion process. The synthesized CdS was characterized using X-ray diffraction (XRD), field mission scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscopy (HR-TEM). The by-product assisted combustion synthesis yields CdS nanoparticles with the mixtures of octahedral geometries, hexagonal, and triangle plate morphologies and the sizes were found to be 100 nm to 5 microm. The XRD patterns imply the formation of well crystallized wurtzite CdS. The influence of cadmium and sulfur precursors and microwave irradiation time on the morphology of CdS nanoparticle was also investigated. The cadmium and sulfur precursors strongly influenced the CdS morphology and increasing the microwave irradiation time and intensity has no effect on the CdS morphology. In addition, a plausible mechanism of CdS nanoparticle formation has been proposed in this research.     

柠檬酸络合无焰燃烧法制备尖晶石型LiMn2O4

采用柠檬酸络合无焰燃烧法制备锂离子电池正极材料尖晶石型LiMn2O4，颗粒大小只有10－100nm，晶型完整，电化学性能与国内外商品化的同种材料相当。直流电阻实验显示该材料在低于室温处存在一个相变。采用柠檬酸络合无焰燃烧法可以简化柠檬酸络合反应法的制备工艺，降低其成本。