微乳法制备纳米TiO2 /SiO2的结构及光催化研究

Nanosized TiO₂ and TiO₂/SiO₂ particles were prepared by hydrolysis of tetrabutyl titanate (TBOT) and tetraethyl orthosilicate (TEOS) in the TX-100 reverse microemulsion. These particles were characterized by TG-DSC, XRD, FTIR, TEM，N₂ adsorption-desorption. Their photocatalytic activity was tested by degradation of methyl orange. The result shows that TiO₂/SiO₂ nanoparticles are with a monodispersed spherical phase and a uniform size distribution，and TiO₂ particles are dispersed on the surface of SiO₂. The band for Ti-O-Si vibration in FTIR was observed, the Ti-O-Si bond increased the stability of anatase TiO₂, suppressed the phase transformation of titania from anatase to rutile. And due to the addition of SiO₂, the average size of titania decreased from 38 nm in pure TiO₂ to 5 nm in TiO₂/SiO₂. It was found, under UV light irradiation, TiO₂/SiO₂ particles showed higher activity than pure TiO₂, and TiO₂/SiO₂(1/1) particles showed the highest photocatalytic activity on the photocatalytic decomposition of methyl orange, which was influenced by crystal structure, particle size, crystallinity and Surface area Characteristics.     

梯度材料LiNi0.8Co0.2O2的合成与表征

The gradient composite LiNi_0.8Co_0.2O₂ was synthesized using spherical Ni(OH)₂ particle coated by a sol-gel containing cobalt and lithium. The precursor was examined by DSC-TG. The gradient composite was characterized by SEM, EDS, XPS, XRD and ICP-AES. The XPS, EDS and ICP-AES results show that content of cobalt in the surface is higher than in the center of the spherical particle of the gradient composite. The first discharge specific capacity of the gradient composite sintered at 700 ℃ is 187.3 mAh·g^-1.     

掺钇锆酸锶-TiO2复合光催化剂的制备及性能研究

SrZrO₃ particles were prepared by a co-precipitation method and Sr(Zr_1-xY_x)O_3-δ -TiO₂ composite particles were then synthesized by Sr(Zr_1-xY_x)O_3-δ and titanium dioxide. The composite particles were characterized by XRD, SEM, FTIR and TG-DTA techniques. The photocatalytic degradation of methylene blue (MB) in aqueous solution was used as a probe reaction to evaluate the photocatalytic activity of the composite particles. The effect of the preparation method for SrZrO₃, doping content of yttrium and TiO₂ amount in the composite particles on the photocatalytic activity of composite particles was also discussed. The results show that the methylene blue solution could be completely degraded by Sr(Zr_1-xY_x)O_3-δ -TiO₂ composite particles under UV-light or visible light irradiation. The photocatalytic activity of composite particles was higher than that of pure TiO₂. The fast recombination of photogenerated electrons and holes were restrained by the heterojunction formed in composite particles. The particle of SrZrO₃ prepared by co-precipitation was small, and the photocatalytic activity of composite particles prepared from this kind of SrZrO₃ was higher than that of particles prepared by solid sintering method. The best doping content of yttrium is 5%. The optimal content of TiO₂ in composite particles is 90wt%, 70wt%, respectively under UV-light and visible light irradiation, the degradation rates of MB are 98.8% and 93.5% , respectively after 50 min irradiation.     

纳米晶SnO2粉体的合成

Crystalline tin oxide nanoparticles were synthesized by the direct precipitation from the starting material granulated tin. TG-DTA of the precursor showed a heavy weight loss at about 130℃ accompanied by an endothermic peak， two exothermic peaks above 200℃ accompanied by small weight loss indicated the decomposition and the oxidation of residual NO₃^- ion and PEG. XRD showed that obtained particles agreed well with the determination result of bulk SnO₂. The broadened XRD patterns became sharper as the calcining temperature turned to higher， it was indicated that the growth of the particle was exhibited. The surface area of the particles calcined at 300℃ was 161.1m²·g^-1 and declined as the calcining temperature turned to higher. TEM showed an heavier agglomeration at higher temperature.     

TiO2胶粒在铝合金表面的电泳沉积及所制薄膜的光催化性能研究

TiO₂ membranes were prepared on aluminum-alloy thin plates by electrophoretic deposition and dip coating in a colloid solution of TiO₂, respectively. The photocatalytic activity of TiO₂ membrane was compared using ethylene as reactant, and the crystal and morphological structure of the membrane were characterized by XRD and SEM. The results showed that a more compact membrane with high loading of TiO₂ but lower photocatalytic activity of unit TiO₂ mass was obtained by electrophoresis compared with dip coating method. The addition of polyethylene glycol (PEG) to the sol of TiO₂ could improve the specific photocatalytic activity (ethylene conversion per unit mass TiO₂ and unit area of membrane piece) of the electrophoresis-membrane prepared from the sol, but could not change the specific photocatalytic activity of the dip-coating membrane from the sol. The ethylene conversion on the electrophoresis membrane prepared from the sol containing PEG (50 g·L^-1) was 9 times of that on the dip coating membrane. The effect of PEG on the properties of electrophoresis-membrane of TiO₂ was attributed to the change of electrokinetic properties of sol. Addition of PEG decreased ζ potential value of the sol and the mobility of the sol particle, increased viscidity of the colloid, thus decreasing both the electrophoresis deposition velocity of colloid particles and the electroosmosis velocity of diffuse layer of colloid particles. These favored the formation of a low compact and porous membrane on the electrode in electric field, and thus increasing the availability of TiO₂ in photocatalytic process.     

新型纳米多孔SiO2气凝胶微球材料的制备

A new type of nanoporous SiO₂ aerogel microsphere materials were synthesized by using SiO₂ sols as raw materials in the W/O emulsion formed by the emulsification of Tween-85 and Span-80. The obtained wet gel microspheres were aged by a successive solvent exchanging of alcohol, tetraethylorthosilicate (TEOS)/ethanol solution and ethanol at 60 ℃, and then were dried at ambient pressure to produce SiO₂ aerogel microspheres. The resultant SiO₂ aerogel microspheres were characterized by SEM, TEM and nitrogen adsorption-desorption. The results show that the prepared SiO₂ aerogel microspheres are nanoporous materials with coherent network nanoporous structure consisting of SiO₂ nanoparticles with an average diameter of about 10 nm. The apparent density of a typical sample is 0.4 g·cm^-3, while the specific surface area is 386 m²·g^-1, and the average pore size is 18 nm with the porosity of 84%. Various SiO₂ aerogel microspheres with the apparent particle sizes of 10～200 μm can be synthesized by controlling the stirring speed at 600～2 000 r·min^-1, the volume ratio of water/oil from 0.10 to 0.30, and the weight ratio of Tween-85/Span-80 less than 0.40.     

Nafion? / TiO2复合膜的质子传导性能研究

Nafion^® / TiO₂ composite membranes were prepared by in-situ chemical reaction method using Ti(OC₄H₉)₄ and Nafion^® 117 as raw materials. The membranes were characterized by UV, FTIR-ATR and XRD, respectively. Methanol permeability and water uptake were investigated as a function of TiO₂ contents. The conductivity of the membranes was measured under water vapor pressure (2.644 7 kPa) or in dry atmospheres. The XRD results showed that the titanium dioxide in Nafion^® membranes were crystallized in anatase phase with an average crystaline diameter of 3.0 nm. The water uptake of the composite membranes was larger than that of the pure Nafion^® membrane when the TiO₂ loading was within 14wt%. The methanol permeability of the membrane decreased as the TiO₂ loading increased. The addition of 3wt% TiO₂ to Nafion^® membranes improved the conductivity in dry measurement conditions. The proton conductivity of the composite membrane increased greatly after the hydrothermal treatment at 160 ℃ for 2 hours.     

碳包覆LiFePO4的一步固相法制备及高温电化学性能

Carbon coated LiFePO₄ cathode material was synthesized by one-step solid-state reaction and characterized by X-ray diffraction (XRD), field-emission-scanning electron microscope (FESEM). Electrochemical performances of the material as cathode in lithium-ion battery were investigated at medium and elevated temperature (30 and 55 ℃) by galvanostatic charge-discharge and A.C. impedance tests. The results show that carbon coated LiFePO₄ powder exhibits a well-crystallized olivine structure and spherical morphology with an average particle size of about 500 nm. Galvanostatic charge-discharge tests show that the reversible discharge capacity at 1 C and 1.5 C rates was improved from 121 and 105 mAh·g^-1 at 30 ℃ to 136 and 123 mAh·g^-1 at 55℃, respectively, while the enhancement of high temperature on electrochemical performance is less obvious at a rate lower than 0.5 C. Impedance spectra analyses indicate that the cathode material has a remarkably higher lithium-ion diffusivity at 55 ℃ than that at 30 ℃, which improves the electrochemical performance at high temperature.     

预氧化固气法合成LiNiO2的研究

LiNiO₂ was prepared by reaction of stoichiometric amounts of thoroughly-mixed LiOH·H₂O and preoxidation nanometer-scale Ni₃O₂(OH)₄ powders in O₂ at the temperature of 700℃ for 6h. The products were tested by XRD， XPS， SEM and electrochemistry methods. It was shown that product was LiNiO₂ single-phase， and the valence of nickel was +3; the average size of it was 40nm; its initial charge specific capacity is 168mAh·g^-1 and the coulomb efficiency is 90%; the second charge specific capacity is 160mAh·g^-1 and the coulomb efficiency is 96%.     

H2在非晶态合金Ni40Fe40P20表面的吸附行为

With the level of B3LYP/Lanl2dz of density functional theory and advisable adsorption models designed, the adsorption properties of the most stable cluster of Ni₂Fe₂P were calculated, and four stable configurations with the adsorption of hydrogen were gained. The geometries and HOMO contributions of 3d orbital of metal atoms and energy level properties of adsorption configurations were concerned and their Infrared Spectrum were simulated and predicted. The bond lengths and bond orders and vibration frequencies concerned synthetically, the adsorption mechanisms of hydrogen molecular on amorphous alloys Ni₄₀Fe₄₀P₂₀ surfaces were discussed in the microcosmic aspect. The hydrogen molecules adsorbing on the clusters were dissociated. In the clusters′ Infrared Spectrums of hydrogen adsorption, there were the vibration peaks with the frequency less than 500 cm^-1 caused by metal atoms and other vibration peaks with the frequency more than 500 cm^-1 caused by hydrogen atoms. Compared with the energy level DOS of the clusters before and after adsorption, it was found, that the new adsorption activity sites generated after the adsorption of hydrogen, as well as easy way for metal atoms providing electrons and participating subsequence reactions were gained.     

g-C3N4/Bi2O2CO32D纳米片复合材料的制备及可见光催化性能研究

采用自组装和化学沉淀法分别制得两种可见光驱动复合材料石墨相氮化碳/碳酸氧铋(g-C_3N_4/Bi_2O_2CO_3).采用X射线衍射光谱(XRD),紫外可见光谱、扫描电镜(SEM)、N_2吸附、电化学阻抗谱(EIS)和X射线光电子能谱(XPS)等分析手段对制备的催化剂进行了表征.结果表明,制备方法对纳米复合材料的晶相、形态及光学性能没有影响,但是影响g-C_3N_4和Bi_2O_2CO_3之间的相互作用力,导致光生电子-空穴对的分离速率存在显著差异.以可见光驱动苯酚和罗丹明B的降解实验为探针反应检测催化剂的光催化性能.实验结果表明自组装法得到的异质结催化剂中相互作用力更强,催化效果最高.O_2-是罗丹明B降解反应的主要活性物种,染料的光敏化、Bi_2O_2CO_3与g-C_3N_4综合效应,导致光生载流子电荷分离效率更高.     

SnO_2改性TiO_2对V_2O_5-WO_3/TiO_2催化剂结构和SCR性能影响

采用共沉淀法将SnO_2组分掺入到V_2O_5-WO_3/TiO_2催化剂载体TiO_2中,并通过多种物理化学手段,考察了不同SnO_2掺入量时对催化剂结构,表面分散物种和SCR性能影响.结果表明,SnO_2掺入到TiO_2中,元素Sn与Ti以Sn—O—Ti键形式相互作用,促进锐钛矿型TiO_2向金红石型TiO_2转变.在特定条件下,VO_x与WO_x物种和SnTi氧化物之间以V—O—Ti(Sn)和W—O—Ti(Sn)键形式相互作用,提高了VO_x物种可还原能力、促进了具有更多B酸酸量四面体WOx物种和V~(5+)物种生成.VW/SnTi催化剂表面VO_x物种与WO_x物种之间的相互作用更强.因此,VW/SnTi催化剂具有更好的SCR活性.     

Spectroscopic properties of guanidinium zinc sulphate [C(NH2)3]2Zn(SO4)2 and ab initio calculations of [C(NH2)3]2 and HC(NH2)3

Raman and FTIR spectra of guanidinium zinc sulphate [C(NH₂)₃]₂Zn(SO₄)₂ are recorded and the spectral bands assignment is carried out in terms of the fundamental modes of vibration of the guanidinium cations and sulphate anions. The analysis of the spectrum reveals distorted SO₄²⁻ tetrahedra with distinct S–O bonds. The distortion of the sulphate tetrahedra is attributed to Zn–O–S–O–Zn bridging in the structure as well as hydrogen bonding. The CN₃ group is planar which is expressed in the twofold symmetry along the C–N (1) vector. Spectral studies also reveal the presence of hydrogen bonds in the sample. The vibrational frequencies of [C(NH₂)₃]₂ and HC(NH₂)₃ are computed using Gaussian 03 with HF/6-31G* as basis set.     

Catalytic oxidation of no to NO2 over Cr/TiO2 and Cu/TiO2 under oxidizing atmosphere

The catalytic activity of Cr/TiO₂ and Cu/TiO₂ for the oxidation of NO under an oxidizing atmosphere has been examined. Both catalysts had excellent ability for the oxidation of NO to NO₂ in the temperature range of 350–400°C.     

硝酸镁在γ-Al2O3上的热分解及MgO/γ-Al2O3

研究了不同载量时Mg(NO     

Cp2TiCl2 catalyzed one-pot synthesis of n-Bu3GeH from GeCl4

The reaction of GeCl₄ with n-BuMgCl in presence of a catalytic amount of Cp₂TiCl₂ gives n-Bu₃GeH and n-Bu₄Ge in ca. 70 and 25% yield, respectively. This method provides an industrially feasible one-pot synthesis for Bu₃GeH and Bu₄Ge. The reaction temperature and stoichiometry seem to be important in the distribution of the products. Apart from elemental analysis these compounds have been characterized by comparing their boiling points, NMR spectral data and GC assay with that of the authentic samples.     

TiO2/SnO2复合光催化剂的耦合效应

采用改进的sol gel技术制备TiO2/SnO2耦合型半导体光催化剂,利用XRD、气相色谱 仪、粒度仪和表面光电压装置等研究了耦合型半导体光催化机理和光催化效率的影响因素, 并通过降解甲醛探讨其在空气污染治理中的作用.实验结果表明,添加20 ％(mol) SnO2的复 合半导体光催化剂,其光催化效率比纯TiO2高一倍以上.据实验结果和粒子紧密堆积原理,提 出强耦合效应和弱耦合效应的光催化反应模型,并用此模型较好地解释了TiO2/SnO2复合型半 导体光催化剂的光催化效率随SnO2含量变化规律.     

CeO2改性Ag-V2O5/TiO2催化剂的甲基吡啶氧化脱甲基性能

以锐钛矿TiO_2为载体,考察了CeO_2改性对Ag-CeO_2-V_2O_5/TiO_2催化3-甲基吡啶氧化脱甲基性能的影响,并优化了催化剂组成与制备条件.结果表明:Ce掺杂改性不仅能够与V物种作用形成Ce VO_4,而且促进V_2O_5分散,改善活性组分的氧化还原性能,从而提高3-甲基吡啶脱甲基转化率与选择性,改善Ag-V_2O_5/TiO_2催化性能.适宜的催化剂组成为V_2O_5负载量15%,Ce/V的摩尔比0.33,Ag质量分数1.0%.过高的焙烧温度将导致TiO_2载体向金红石型转变,Ag-CeO_2-V_2O_5/TiO_2适宜制备条件为450℃焙烧4 h.     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…     

Conversion of NO in NO/N2, NO/O2/N2, NO/C2H4/N2 and NO/C2H4/O2/N2 Systems by Dielectric Barrier Discharge Plasmas

An experimental study on the conversion of NO in the NO/N₂, NO/O₂/N₂, NO/C₂H₄/N₂ and NO/C₂H₄/O₂/N₂ systems has been carried out using dielectric barrier discharge (DBD) plasmas at atmospheric pressure. In the NO/N₂ system, NO decomposition to N₂ and O₂ is the dominating reaction; NO conversion to NO₂ is less significant. O₂ produced from NO decomposition was detected by an on-line mass spectrometer. With the increase of NO initial concentration, the concentration of O₂ produced decreases at 298 K, but slightly increases at 523 K. In the NO/O₂/N₂ system, NO is mainly oxidized to NO₂, but NO conversion becomes very low at 523 K and over 1.6% of O₂. In the NO/C₂H₄/N₂ system, NO is reduced to N₂ with about the same NO conversion as that in the NO/N₂ system but without NO₂ formation. In the NO/C₂H₄/O₂/N₂ system, the oxidation of NO to NO₂ is dramatically promoted. At 523 K, with the increase of the energy density, NO conversion increases rapidly first, and then almost stabilizes at 93–91% of NO conversion with 61–55% of NO₂ selectivity in the energy density range of 317–550 J L⁻¹. It finally decreases gradually at high energy density. A negligible amount of N₂O is formed in the above four systems. Of the four systems studied, NO conversion and NO₂ selectivity of the NO/C₂H₄/O₂/N₂ system are the highest, and NO/O₂/C₂H₄/N₂ system has the lowest electrical energy consumption per NO molecule converted.