Synthesis of Mn3O4 nanoparticles by thermal decomposition of a [bis(salicylidiminato)manganese(II)] complex

The present investigation reports on the novel synthesis of Mn₃O₄ nanoparticles using thermal decomposition and their physicochemical characterization. The Mn₃O₄ nanoparticle powder has been prepared using [bis(salicylidiminato)manganese(II)] as a precursor. The effect of oleyl amine and triphenylphosphine on the particle morphology has been investigated. Transmission electron microscopy (TEM) analysis demonstrated Mn₃O₄ nanoparticles with an average diameter of about 25 nm. The structural study by X-ray diffraction (XRD) indicates that these nanoparticles have a pure tetragonal phase. The phase pure samples were characterized using X-ray photoelectron spectroscopy (XPS) for both Mn 2p and Mn 3s levels. The values of binding energies are consistent with related values reported in the literature.     

Hydrophilic and hydrophobic nano-sized Mn3O4 particles

Mn₃O₄ Hausmanite nanoparticles were prepared in aqueous solution by using metallic salt and hydrazine as precursor and reducing agent, respectively. The crystallite sizes ranged from 10 to 20 nm and the particle diameter distribution was very narrow and estimated between 20 and 30 nm. Influence of some parameters such as temperature, time of reaction, surfactant nature was studied for a synthesis in an aqueous medium. The as-made manganese oxides particles could be dispersed in an organic solvent containing stabilizing agents, according to perform the synthesis in an H₂O/n-hexan two-phase medium. These nanoparticles were characterized by X-ray diffraction, infrared spectroscopy, scanning and transmission electron microscopies and nitrogen absorption measurements.     

氧化钛包覆对LiCo0.2Ni0.4Mn0.4O2结构和性能的影响

采用SEM、 XRD、 XPS、恒电流充放电等方法研究了不同量的氧化钛包覆对LiCo_0.2Ni_0.4Mn_0.4O₂结构和电化学性能的影响。结果表明，0.3mol%氧化钛包覆能显著改善LiCo_0.2Ni_0.4Mn_0.4O₂的循环性能、倍率放电能力及高截止电压(3.0～4.5 V)下的循环性。XPS数据表明氧化钛包覆能明显的抑制样品表面的氧化活性，从而减少了电极材料表面与电解液的反应，改善了LiCo_0.2Ni_0.4Mn_0.4O₂的电化学性能。     

溶胶凝胶法合成Li3V6O16及其电化学性能研究

本文以双氧水为配位剂,以CH3COOLi·2H2O和V2O5为原料,采用溶胶凝胶法合成了一种新型的晶体Li3V6O16。随后分别采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和电子衍射(SAED)、X光电子能谱(XPS)和充放电测试等手段对材料进行了表征。SEM观察表明,产物主要是表面比较光滑的纳米片状晶体,TEM和SAED研究都证实了XRD和SEM的研究结果。充放电测试结果表明,该物质具有较高的比容量、良好的可逆性和循环稳定性。     

Structural characterization and photocatalytic activity of hollow binary ZrO2/TiO2 oxide fibers

The formation of hollow binary ZrO₂/TiO₂ oxide fibers using mixed precursor solutions was achieved by activated carbon fibers templating technique combined with solvothermal process. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption, X-ray photoelectron spectroscopy (XPS), UV-vis, and infrared (IR) spectroscopy. The binary oxide system shows the anatase-type TiO₂ and tetragonal phase of ZrO₂, and the introduction of ZrO₂ notably inhibits the growth of TiO₂ nanocrystallites. Although calcined at 575 °C, all hollow ZrO₂/TiO₂ fibers exhibit higher surface areas (>113 m²/g) than pure TiO₂ hollow fibers. The Pyridine adsorption on ZrO₂/TiO₂ sample indicates the presence of stronger surface acid sites. Such properties bring about that the binary oxide system possesses higher efficiency and durable activity stability for photodegradation of gaseous ethylene and trichloromethane than P25 TiO₂. In addition, the macroscopic felt form for the resulting materials is more beneficial for practical applications than traditional catalysts forms.     

Hydrothermal synthesis and magnetic properties of RMn2O5 (R=La, Pr, Nd, Tb, Bi) and LaMn2O5+δ

RMn₂O₅ (R=La, Pr, Nd, Tb, Bi) crystallites were prepared by a mild hydrothermal method and characterized by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy (XPS) and magnetic measurement. The formation of manganates was sensitive to the alkalinities and Mn-containing precursors of the reaction mixtures. This family of manganates is isostructural and has a space group of Pbam. The magnetic measurements for RMn₂O₅ showed an antiferromagnetic transition. The strong irreversibility between the ZFC and FC curves indicated a helicoidally magnetic structure below 40 K. The max d.c. susceptibilities of LaMn₂O_5+δ (δ=0.01, 0.06, 0.08, 0.16, 0.17) were found to be variable and the excess oxygen (δ) in the compounds was influenced by the alkalinity used in the hydrothermal synthesis.     

CuTAPc-Fe3O4纳米复合粒子及其漆酶固定化研究

漆酶的固定化研究对基于漆酶催化的光纤生物传感器具有十分重要的意义. 制备了四氨基酞菁铜(CuTAPc)-Fe₃O₄纳米复合粒子, 并用红外(IR)、场发射扫描电镜(FEG-SEM)、X射线衍射(XRD)、能谱、粒径仪等对其进行了表征. 结果表明形成了以CuTAPc包覆在Fe₃O₄纳米粒子表面的纳米复合粒子, 粒子呈现不规则球形, 且分布均匀, 粒子平均粒径在50 nm左右. 用此纳米复合粒子通过戊二醛交联法固定了漆酶, 固定后的酶比游离酶具有更好的贮存稳定性及操作稳定性. 这为研制高性能的光纤生物传感器打下了较好的基础.     

Synthesis of layered cathode material Li[CoxMn1−x]O2 from layered double hydroxides precursors

Cathode materials Li[Co_xMn_1−x]O₂ for lithium secondary batteries have been prepared by a new route—precursor method of layered double hydroxides (LDHs). In situ high-temperature X-ray diffraction (HT-XRD) and thermogravimetric analysis coupled with mass spectrometry (TG-MS) were used to monitor the structural transformation during the reaction of CoMn LDHs and LiOH·H₂O: firstly the layered structure of LDHs transformed to an intermediate phase with spinel structure; then the distortion of the structure occurred with the intercalation of Li⁺ into the lattice, resulting in the formation of layered Li[Co_xMn_1−x]O₂ with α-NaFeO₂ structure. Extended X-ray absorption fine structure (EXAFS) data showed that the Co-O bonding length and the coordination number of Co were close to those of Mn in Li[Co_xMn_1−x]O₂, which indicates that the local environments of the transitional metals are rather similar. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation state of Co and Mn. The influences of Co/Mn ratio on both the structure and electrochemical property of Li[Co_xMn_1−x]O₂ have been investigated by XRD and electrochemical tests. It has been found that the products synthesized by the precursor method demonstrated a rather stable cycling behavior, with a reversible capacity of 122.5 mAh g⁻¹ for the layered material Li[Co_0.80Mn_0.20]O₂.     

Hydrothermal synthesis of monodisperse Fe3O4 nanoparticles based on modulation of tartaric acid

In this paper, monodisperse Fe₃O₄ nanoparticles with single crystalline structure were synthesized via a facile environment-friendly method. And the size of the nanoparticles ranges from 10 nm to 15 nm. As-synthesized Fe₃O₄ were characterized by X-ray diffraction instrument (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) spectrometer and field emission transmission electron microscope (FE-TEM). The effect of tartaric acid (TA) amount on products was investigated by XRD and TEM. The results indicated that TA could commendably modulate the crystalline phase, morphology and size of nanometer Fe₃O_4. A possible generated mechanism of Fe₃O₄ crystals was proposed in virtue of UV–vis absorption spectra. Besides, the magnetic properties of as-synthesized Fe₃O₄ were detected.     

Preparation of Mn2O3 and Mn3O4 nanofibers via an electrospinning technique

Thin PVA/manganese acetate composite fibers were prepared by using sol-gel processing and electrospinning technique. After calcinations of the above precursor fibers, Mn₂O₃ and Mn₃O₄ nanofibers with a diameter of 50-200 nm could be successfully obtained. The fibers were characterized by TG-DTA, Scanning electron microscopy, FT-IR, WAXD, respectively. The results showed that the crystalline phase and morphology of nanofibers were largely influenced by the calcination temperature.     

A facile two-step modifying process for preparation of poly(SStNa)-grafted Fe3O4/SiO2 particles

This article reports the synthesis of the poly(sodium 4-styrenesulfonate)-grafted Fe₃O₄/SiO₂ particles via two steps. The first step involved magnetite nanoparticles (Fe₃O₄) homogeneously incorporated into silica spheres using the modified Stöber method. Second, the modified silica-coated Fe₃O₄ nanoparticles were covered with the outer shell of anionic polyelectrolyte by surface-initiated atom transfer radical polymerization. The resulted composites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive microscopy (EDS), Fourier transform-infrared (FT-IR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and vibration sample magnetometer (VSM). The XRD results indicated that the surface modified Fe₃O₄ nanoparticles did not lead to phase change compared with the pure Fe₃O₄. TEM studies revealed nanoparticles remained monodisperse. The detection of sulfur and sodium signals was a convincing evidence that sodium 4-styrenesulfonate was grafted onto the surface of the magnetic silica in XPS analysis. Finally, super-paramagnetic properties of the composite particles, and the ease of modifying the surfaces may make the composites of important use in mild separation, enzyme immobilization, etc.     

Sol-gel preparation and spectroscopic study of the pyrophanite MnTiO<Subscript>3</Subscript> nanoparticles

The nanosized xerogel of titanium dioxide (TiO₂) and manganese oxides (MnO₂, Mn₂O₃, Mn₃O₄) was prepared by the sol-gel method using manganese chloride (MnCl₂·4H₂O) and titanium isopropoxide (Ti(O-iPr)₄) as precursors in cetyltrimethylammonium bromide (CTAB)/ ethanol/H₂O/HCl micelle solutions, following the calcinations of the produced powders at difference temperatures. The nanostructure and phase composition of these nanoparticles were characterized with X-ray powder diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). The spectroscopic characterizations of these nanoparticles were also done with UV-Vis spectroscopy and laser Raman spectroscopy (LRS). XRD patterns show that the pyrophanite MnTiO₃ phase was formed at the calcinations temperature of 900°C. The TEM images show that the nanoparticles are almost spherical or slight ellipose and the sizes are 50 nm on average. The UV-Vis spectra show that the nanosized MnTiO₃ have significant absorption bands in the visible region. There are new absorption peaks of MnTiO₃ nanoparticles in LRS compared with the pure TiO₂ powder.     

掺F影响LiNi0.8Co0.1Mn0.1O2结构和性能的微观机制

以氟化锂为氟源,通过高温固相法合成了F掺杂的LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2。采用X射线衍射仪(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)和电化学测试等手段研究F影响LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2结构和性能的微观机制。结果表明:适量F掺杂可以提高正极材料的放电比容量,改善其倍率性、循环性和热稳定性。当F掺杂量(物质的量分数)为1.5%时,材料的综合电化学性能最优,初始放电比容量(0.2C)和50周循环容量保持率(1C)分别由原始的174.0 mAh·g~(-1)(78.7%)提高到178.6 mAh·g~(-1)(85.7%)。LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2材料性能的改善可归因于F能够增强过渡金属层、锂层与氧层之间的结合力,提高材料的结构稳定性。此外,F掺杂还有利于降低电化学反应中的界面电阻和电荷转移阻抗。     

Preparation and characterization of pure single-phase BiFeO3 nanoparticles through thermal decomposition of the heteronuclear Bi[Fe(CN)6]·5H2O complex

The heteronuclear Bi[Fe(CN)₆]·5H₂O complex was synthesized and single-phase perovskite-type BiFeO₃ nanoparticles with an average size of 30 nm were obtained by its decomposition at 600 °C. The complex and its decomposition products were analyzed using elemental analysis, thermal analysis (TGA/DTA/DSC), X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR), UV–Vis spectroscopy, BET specific surface area measurement, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and magnetic measurements. The magnetic measurement confirms that the product shows a ferromagnetic order at room temperature, which may be ascribed to the size confinement effect. The DTA and DSC results confirm the multiferroic nature of the BiFeO₃ nanoparticles with Neel and Curie points at 372 and 825 °C, respectively. The BiFeO₃ prepared by this method could be an appropriate visible-light photocatalytic material due to its strong absorption band in the visible region. This method is simple, low-cost, safe and also suitable for industrial production of high purity perovskite-type BiFeO₃ nanoparticles for electromagnetic applications.     

陈化体系组成对Ce0.65Zr0.35O2储氧材料性能的影响

采用共沉淀法制备了Ce_0.65Zr_0.35O₂(CZ)储氧材料, 在传统的水陈化体系中引入了乙醇, 研究了乙醇的加入对CZ储氧材料性能的影响. 对所制备样品进行了傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)、粉末X射线衍射(XRD)、扫描电镜(SEM)、N₂吸附-脱附、储氧量(OSC)和H₂程序升温还原(H₂-TPR)的表征, 并考察了以CZ储氧材料为载体制备的单钯催化剂的三效性能. 结果表明, 乙醇引入陈化体系对样品的结构和性能有显著影响. 以醇水共存体系陈化制备的CZ储氧材料颗粒小、堆积松散、孔径分布宽、孔容大, 具有优异的储氧性能和热稳定性, 经1000 °C焙烧后, 比表面积为29.3 m²·g^-1, 储氧量仍高达520 μmol·g^-1. 以此为载体制备的单钯催化剂, 空燃比操作窗口宽, 对C₃H₈、CO、NO的转化明显优于水陈化体系制备的储氧材料所制备的催化剂.     

CTAB-assisted synthesis of mesoporous F-N-codoped TiO2 powders with high visible-light-driven catalytic activity and adsorption capacity

This article describes the preparation of mesoporous rod-like F-N-codoped TiO₂ powder photocatalysts with anatase phase via a sol-gel route at the temperature of 373 K, using cetyltrimethyl ammonium bromide (CTAB) as surfactant. The as-prepared photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance spectra (UV-vis DRS). The results showed that the photocatalysts possessed a homogeneous pore diameter and a high surface area of 106.3-160.7 m³ g⁻¹. The increasing CTAB reactive concentration extended the visible-light absorption up to 600 nm. The F-N-codoped TiO₂ powders exhibited significant higher adsorption capacity for methyl orange (MO) than that of Degussa P25 and showed more than 6 times higher visible-light-induced catalytic degradation for MO than that of P25.     

一锅法制备Co3O4/g-C3N4复合光催化剂及其光催化性能

以三聚氰胺和六水合氯化钴为原料,一锅法制备Co_3O_4负载的多孔石墨相氮化碳(Co_3O_4/g-C_3N_4)复合光催化材料。采用X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见漫反射光谱(UV-Vis DRS)、光致发光光谱(PL)等手段对其结构和光学特性进行表征。以盐酸四环素(TC)为目标污染物,评价了不同负载量Co_3O_4/g-C_3N_4复合光催化剂的可见光催化性能。结果表明,所制备的Co_3O_4/g-C_3N_4复合光催化剂为多孔结构,其比表面积较大,并在可见光区域具有显著的吸收。利用原位生成的Co_3O_4纳米粒子在氮化碳表面形成异质结构,可有效转移光生载流子,降低光生电子-空穴的再结合率,从而提高光催化活性。并且存在最佳Co_3O_4复合量,当六水合氯化钴加入量为三聚氰胺的8%(w/w)时,所制备的复合光催化剂CoCN-8具有最佳的光催化性能。在可见光的照射下,60 min内可降解85%的TC,而同样条件下,纯g-C_3N_4仅降解23%的TC。     

Polypyrrole/γ-Fe2O3 magnetic nanocomposites synthesized in supercritical fluid

Polypyrrole/iron oxide (PPy/γ-Fe₂O₃) nanocomposites were synthesized by in situ oxidative polymerization of pyrrole in the presence of surface modified γ-Fe₂O₃ in supercritical carbon dioxide (scCO₂). The structural properties of nanocomposite particles thus obtained were characterized by FT-IR, thermal analysis (TGA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). It was found that ca. 50 nm γ-Fe₂O₃ nanoparticles were well dispersed in PPy powder in TEM pictures. X-ray photoelectron spectroscopy (XPS) analysis also support that all γ-Fe₂O₃ nanoparticles are encapsulated by PPy. Magnetic property of the nanocomposites was measured by SQUID, which indicated that the nanocomposites are superparamagnetic. The effects of different loadings of γ-Fe2O3 on the polymerization were also investigated.     

Effect of TiO2-coating on structure and electrochemical performance of LiCo0.2Ni0.4Mn0.4O2

LiCo_0.2Ni_0.4Mn_0.4O₂, as the cathode material for lithium ion batteries, was modified by TiO₂-coating. The effect of TiO₂-coating on the structure and electrochemical performance of LiCo_0.2Ni_0.4Mn_0.4O₂ was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and galvanostatic charge-discharge tests. The results suggest that a small amount of TiO₂-coating does not change the crystalline structure, but considerably improves the electrochemical performance of LiCo_0.2Ni_0.4Mn_0.4O₂ in terms of capacity delivery and cyclability. XPS measurements confirm that the improved electrochemical performance is most possibly attributed to a decrease in interaction between the layered material and non-aqueous electrolyte during the charge-discharge processes. __________ Translated from Chinese Journal of Inorganic Chemistry, 2007, 23(5): 753–758 [译自: 无机化学学报]     

Preparation of porous TiO2/silica composites without any surfactants

TiO₂-SiO₂ composites, with high specific surface area (up to 308 m²/g), large pore volume, and narrow distribution with average pore sizes of 3.2 nm, have been synthesized from wollastonite and titanium sulfate in the absence of any surfactants. Calcium sulfate, a microsolubility salt, plays an important role in the formation of pores in this porous TiO₂/silica composite. The microstructure and chemical composition of composite were characterized by X-ray diffractometry (XRD), transmission electron microscopy (TEM) equipped with energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectrometer (XPS) and N₂ adsorption and desorption analysis. The as-prepared porous titanium dioxide-silicon dioxide composites with high specific surface area and well-crystallized anatase contents were used as an efficient photocatalyst.