柠檬酸溶胶凝胶法制备LiCoO2电极材料及其表征

LiCoO₂ precursors of the cathode material for lithium-ion batteries were prepared from lithium hydroxide， basic cobalt carbonate and citric acid by a sol-gel method. The LiCoO₂ samples were obtained by sintering the gel pre-cursors at different temperatures and for different times. The thermal decomposition behavior of the gel precursors was examined by means of thermo-gravimetric analysis and differential thermal analysis using a PCT-IA thermal analyzer system. Their structures and morphologies were characterized by powder XRD and SEM techniques. It was found that using citric acid realized that the formation of LiCoO₂ crystal can be clearly differentiated to the nucle-ation and growth processes of the crystals; furthermore， the crystal size can be controlled. Electrochemical tests using the LAND BT1-10 test system showed the electrochemical performance of the material is affected by its in-tegrity and stability.     

球形Gd2O3∶Eu纳米发光材料的制备

Spherical nanometer Gd₂O₃∶Eu luminescent materials were prepared by homogeneous precipitation method, and the properties were studied also. TG, FTIR and XRD analysis showed that the precursor was carbonate, the cubic Gd₂O₃was obtained after calcination. TEM photographs indicated that the samples were spherical and well dispersed with nanometer and submicrometer size of 200～300 nm which is the nanoparticles’ aggregate. The mechanics of agglomerating growth is also discussed. ED photograph showed that the particle was crystalline. The PL analysis exhibited that CTB band of nanometer Gd₂O₃∶Eu was of 17 nm red shift to bulk materials, and the emission peak was broadened due to the surface and interface effect of nanocrystals.     

电镀烧结法制备Ti/SnO2-Sb2O4电极的研究

The Ti/SnO₂-Sb₂O₄ electrode has been prepared by the electroplate-sinter method. The effect of SbCl₃ adding amount and sintering temperature on its electrode lifetime and oxygen evolution potential were investigated by means of EDX, SEM and XRD analysis. The results indicated that the electrode appeared the best performance when the SbCl₃ adding amounts was 0.2g and the sintering temperature was 550℃. In optimized conditions Ti substrate was entirely covered by SnO₂-Sb₂O₄ and the combinations among them were tight. Due to the use of electroplate method, the electrical conductivity, the oxygen evolution potential and the electrode lifetime were increased, so the elec-tro-catalytic activity and the electrochemical stability of the prepared electrode were found to be superior.     

水菱钇型碳酸钕的形成及聚甘油脂肪酸酯对结晶的影响

Amorphous Neodymium carbonate was prepared by the precipitation reaction of neodymium chloride with ammonium bicarbonate in solution, and then aged at 60 ℃ to form crystalline neodymium carbonate. The feed molar ratio of n_(NH4HCO3)/n_(NdCl3 was 2.5, and the precipitation was carried out with or without addition of polyglyceryl fatty acid ester (PGFAE). The phase type and morphology of crystalline neodymium carbonates were examined by XRD and SEM, and the effect of PGFAE on the crystallization speed was investigated by volume change in deposit layer and in situ pH determination. The content of neodymium and chloride in crystals was analyzed, and the crystallization reaction or crystal growth characteristics were discussed. It was found that all the crystalline neodymium carbonates were tengerite type, and contained less crystalline water and chloride than that of lanthanite type neodymium carbonate crystallized at room temperature, which is beneficial to the production of neodymium carbonate with higher neodymium and lower chloride content. The addition of PGFAE not only could eliminate the foam formed during precipitation, but also could shorten crystallization time, and form large radiative-like shape conglomeration by the irregulative linkage of one dimension needle crystals. It is also suggested that the morphology and the chloride content of neodymium carbonate were dependent on the structure and crystal growth characteristics.     

锂离子电池正极材料LiMn2O4的合成与晶体结构（英）

Spinel LiMn₂O₄ powders were prepared using two-step synthesis method consisting of solid-state reaction method and citrate modified sol-gel method. The effects of the calcination temperature and the Li/Mn ratio of raw materials were studied on the physicochemical and electrochemical properties of the spinel LiMn₂O₄ powders, such as crystallinity, lattice constant and density. The title compound was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Polycrystalline LiMn₂O₄ powers calcined at 750 ℃ were found to be composed of very uniformly-sized microcrystal with an average particle size of 300 nm. The improvement in electrochemical properties was mainly attributed to the process of re-grinding by absolute alcohol.     

LB膜诱导Ba(NO3)2晶体取向生长

In this work, Ba(NO₃)₂ crystals with single crystal face were induced by using the the method of bio-mimetic mineralization and double LB films of behenic acid (BA) as the template. The crystals were characterized by Scanning Electron Microscope (SEM) and X-Ray Diffraction (XRD). The crystals were observed in regular square shape with uniform size about 5～8 μm by SEM, and they were found by XRD to grow along the (111) plane. From these experiments, we can conclude that the good selection of the (111) crystal face of Ba(NO₃)₂ is due to the electrostatic interactions , the match between this crystal face and the definite lattice structure of the LB films.     

无氨湿法制备纳米晶In2O3及表征

Preparation of In₂O₃nano-scale powders by ultrasonic and homogeneous precipitation, using metal In and urea as raw materials, was reported for the first time, while the effects of reaction temperature, the ratio of the materials and the pH etc. on the preparation was dicussed. This method can be operated and industrialized easily with very low cost． The structural properties of precursor and In₂O₃were characterized by TG-DTA, XRD, ESCA and TEM. The results show that In₂O₃produced are very pure, monophase and spherical nano-scale powders with average size of 25 nm.     

Fabrication of Tubular Structure Agglomerates of Calcium Carbonate by Using Collodion Film

A novel and simple method for preparing tubular structure agglomerates of calcium carbonate (CC-tube) is described. Calcium chloride and sodium carbonate aqueous solutions were used as reactants separated by a collodion film (a nitrocellulose material) in aqueous solution. The effects of the concentrations of calcium chloride and sodium carbonate aqueous solutions on the morphology and phase structure of the as-obtained samples were investigated. The CC-tube growth was prevented with the increase of reactant concentration from 0.5 to 1.0 mol•L－1. Compared with Na2CO3 aqueous solution, it is favourable to grow calcite crystals in CaCl2 aqueous solution. The products were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron- microscopy.     

Li4Ti5O12溶胶-凝胶法合成及其机理研究

The precursors of Li₄Ti₅O₁₂ were prepared from tetrabutyl titanate and lithium acetate by sol-gel process. The Li₄Ti₅O₁₂ samples were synthesized by calcining the gel precursors at 400～900 ℃ in air for 6～20 h. Its reaction mechanism was investigated by infrared spectroscopy(IR), thermogravimetry(TG) and X-ray diffraction(XRD). The effects of sinter-temperature, calcination-time and thermal-treatment for the products were discussed. The samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM). The results showed that the single-phase products were obtained by calcining the gel precursors at 800 ℃ in air for 20 h, the sinter-temperature was lower than that of solid-state method, the particles were narrowly distributed, well crystallized with a size range from 0.3μm to 0.5 μm.     

N 掺杂TiO2光催化剂的制备及其可见光活性研究

A visible-light-active photocatalyst was prepared by calcination of the hydrolysis product of tetrabutyl titanate with ammonia as precipitant. The photocatalyst was characterized by X-ray diffraction (XRD), UV-Vis diffuse reflection spectra (DRS), thermal gravimetric-differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM). The color of the photocatalyst was yellow and could absorb light wavelength under 550 nm as measured by DRS. The catalyst calcined at higher temperature will give lower absorbance for visible light. Structures of the sample were characterized mainly to be anatase by XRD except for the sample calcined at 700 ℃ which gave mixtures of anatase and rutile. TG-DTA results showed that temperature for anatase formation was 415 ℃. XPS results showed that doped-nitrogen was presented in the sample, they are important to show visible-light absorbency. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants, the results showed that over 90% of phenol could be degraded under visible light using N/TiO₂ as the catalyst after 4 hours reaction. Almost the same activity was found for the TiO₂ photocatalyst calcined at different temperature under sunlight but activities were different when the treatment was under UV light.     

铁饼状碳酸钙的制备及性能研究

本文以氯化钙和氨水的混合溶液为水相,聚氧乙烯辛基苯酚醚-10(OP-10)为表面活性剂,正辛醇为助表面活性剂,环己烷为油相配制了反相微乳液。并通过向其中通入CO 2气体制备微/纳米碳酸钙,得到了铁饼状的微米碳酸钙。采用扫描电子显微镜(SEM),X射线粉末衍射(XRD)和傅里叶变换红外光谱(FTIR)表征了微米碳酸钙的形貌和晶型结构。初步探讨了铁饼状微米碳酸钙的形成机理。     

接枝改性碳酸钙及其在聚合物中的应用研究

介绍了近年来碳酸钙表面接枝改性的研究进展,讨论了自由基接枝聚合、辐照接枝聚合和力化学表面接枝聚合及偶联剂预处理与辐照并用接枝聚合改性方法。其中重点讨论了最新研究的偶联剂预处理与辐照并用接枝改性纳米碳酸钙的方法。用此方法制备的聚合物/纳米碳酸钙纳米复合材料在其他力学性能基本不变的情况下,大幅度提高了其缺口冲击强度和断裂伸长率。指出了碳酸钙表面接枝改性应向着提高接枝单体量和采用弹性体单体方面发展。     

牛血清白蛋白Langmuir膜控制方解石形成取向生长的球形微晶

本文以生物矿化模型系统为基础，利用LB技术，采用本体交换的方法，制备了牛血清白蛋白(BSA)Langmuir膜，以更加接近生物矿化的方法研究了BSA Langmuir膜对碳酸钙晶体生长的取向、形貌和晶型的控制作用。XRD分析表明晶体为碳酸钙的方解石晶型，且晶体仅沿(104)晶面有取向生长。SEM分析表明结晶初期碳酸钙以球状的晶体存在，随着时间的延长，BSA对晶体形貌的控制作用逐渐减弱，直到完全不起作用，在结晶后期形成菱方形晶体，但晶体生长取向和晶型始终没有发生变化。说明BSA Langmuir膜对碳酸钙的生长取向、晶型和形貌有较好的控制作用。     

On the structure of amorphous calcium carbonate--a detailed study by solid-state NMR spectroscopy

The calcium carbonate phases calcite, aragonite, vaterite, monohydrocalcite (calcium carbonate monohydrate), and ikaite (calcium carbonate hexahydrate) were studied by solid-state NMR spectroscopy ( (1)H and (13)C). Further model compounds were sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium hydroxide. With the help of these data, the structure of synthetically prepared additive-free amorphous calcium carbonate (ACC) was analyzed. ACC contains molecular water (as H 2O), a small amount of mobile hydroxide, and no hydrogencarbonate. This supports the concept of ACC as a transient precursor in the formation of calcium carbonate biominerals.     

海螺状碳酸钙的可控合成与荧光性能

采用液相沉淀法,以硝酸铋[Bi(NO_3)_3]为添加剂来调控碳酸钙晶体的形状与大小,制备了海螺状碳酸钙粒子.通过扫描电子显微镜(SEM)、X射线衍射仪(XRD)、热重分析仪(TGA)、原子荧光光谱仪(AFS)等对产物的结构和性能进行了表征.结果表明,在60℃条件下,添加20 mL浓度为2 g/L的Bi(NO_3)_3溶液可得到海螺状球霰石型碳酸钙粒子,且其荧光性明显增强.在碳酸钙的成核过程中,Bi~(3+)的加入起到了显著的调控作用.     

Effects of PAA additive and temperature on morphology of calcium carbonate particles

Calcium carbonate particles with various shapes were prepared by the reaction of sodium carbonate with calcium chloride in the absence and presence of a polyacrylic acid (PAA) at 25°C and 80°C, respectively. The as-prepared products were characterized with scanning electron microscopy and X-ray diffraction. The effects of pH, temperatures, aging time and concentration of PAA and CaCO₃ on the crystal form and morphologies of the as-prepared CaCO₃ were investigated. The results show that pH, temperatures, concentration of PAA and CaCO₃ are important parameters for the control of morphologies of CaCO₃. Various crystal morphologies of calcite, such as, plates, rhombohedras, rectangles, ellipsoids, cubes, etc. can be obtained depending on the experimental conditions. Especially, the monodispersed cubic calcite particles can be produced by PAA addition at 80°C. Moreover, higher temperature is beneficial to the formation of monodispersed cubic or rectangular calcite particles. This research may provide new insight into the control of morphologies of calcium carbonate and the biomimetic synthesis of novel inorganic materials.     

pH-dependent release from ethylcellulose microparticles containing alginate and calcium carbonate

Ethylcellulose microparticles containing alginate and calcium carbonate nanoparticles were prepared by spray drying water-in-oil emulsion. Alginate solution (3%) in distilled water was used as an aqueous phase, ethylcellulose solution (5%) in dichloromethane as an oil phase, and sorbitan sesquioleate as an emulsifier. The nanoparticles of calcium carbonate were dispersed into the emulsion. By spray-drying the emulsion, ethylcellulose microparticles containing alginate and calcium carbonate were obtained. When the ratios of alginate to calcium carbonate were 4:1 and 2:1, the pH dependency of the release was marked and the degree of release was suppressed in acidic conditions. When the ratio increased to 1:2, the degree of release increased while the pH-dependent release profiles were maintained. Cavities created by the dissolution of calcium carbonate could account for the increased release.     

Complex-Emulsion synthesis of organo-inorganic amphiphilic sorbents with specific affinity for glucose

Granular organo-inorganic amphiphilic sorbents with specific affinity for glucose were synthesized with the aim of developing selective hemosorbents for efferent therapy of hyperglycemia. The sorbents were prepared in oil/water/oil complex emulsions by copolymerization of 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate on the surface of selenium nanoparticles stabilized with polyvinylpyrrolidone. The phases were stabilized with excess selenium/polyvinylpyrrolidone nanocomplexes. Optimum synthesis conditions ensuring formation of hybrid sorbents with the physicochemical properties required for performing efficient preparative hemosorption and plasma adsorption processes were found. The specific affinity for glucose was reached by modification of these sorbents via imprinting with template glucose molecules in the surface polymer layer and via introduction of boric acid as an affine ligand into the hybrid matrices.     

Layer‐by‐Layer Assembled Nanotubes as Biomimetic Nanoreactors for Calcium Carbonate Deposition

Enzyme‐loaded magnetic polyelectrolyte multilayer nanotubes prepared by layer‐by‐layer assembly combined with the porous template could be used as biomimetic nanoreactors. It is demonstrated that calcium carbonate can be biomimetically synthesized inside the cavities of the polyelectrolyte nanotubes by the catalysis of urease, and the size of the calcium carbonate precipitates was controlled by the cavity dimensions. The metastable structure of the calcium carbonate precipitates inside the nanotubes was protected by the outer shell of the polyelectrolyte multilayers. These features may allow polyelectrolyte nanotubes to be applied in the fields of nanomaterials synthesis, controlled release, and drug delivery.

     

Fabrication of porous graphitic carbon nitride-titanium dioxide heterojunctions with enhanced photo-energy conversion activity

Porous graphite-phase polymeric carbon nitride (GPPCN)/TiO₂ donor-acceptor heterojunction was facilely fabricated through the combination of a template technique with a co-calcination process, which exhibited much higher photoelectric activity compared to pristine carbon nitride and TiO₂. The precursor of porous GPPCN (pGPPCN), porous melem, was prepared by using a green template, calcium carbonate, which could be easily removed by diluted hydrochloride. The pGPPCN/TiO₂ heterojunction was then obtained by the assembly and subsequent co-calcination of TiO₂ nanoparticles with porous melem. The formation of pGPPCN/TiO₂ donor-acceptor heterojunction prepared by this method showed improved surface area and light absorption. Moreover, the composite presented much higher photo-energy conversion activity than those of GPPCN, pGPPCN and TiO₂, which could be mainly ascribed to the high charge carrier separation efficiency. This study provides a new approach for the design and development of various photocatalysts with high efficiency for applications in energy fields.