Synthesis and modification of well-ordered layered cathode oxide LiNi<Subscript>2/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript>

Oxalic-acid-based co-precipitation method was employed to prepare LiNi_2/3Mn_1/3O₂ sample with a high-ordered structure. Li⁺, Ni²⁺ and Mn²⁺ acetates were used as starting materials. The influence of the amount of lithium source in the starting materials on Li⁺ content, disorder of Li⁺-Ni²⁺ ions, and electrochemical performance has been investigated. Rietveld refinement shows that the sample prepared with 20% excess Li-source in the starting materials exhibits a perfect ordered structure. A specific discharge capacity is as high as 172 mAh/g at C/20 in the voltage range of 4.35–2.7 V. However, the cyclability is not satisfactory: about 25.3% fade in capacity was observed over 50 cycles. Chemically stable SiO2 was coated on the surface of LiNi_2/3Mn_1/3O₂ particles. A significant improvement in cyclability was attained with 3 wt% SiO2 coating, which is ascribable to the protection of LiNi_2/3Mn_1/3O₂ particles from being dissolved into the electrolyte.     

Preparation and performance of LiNi0. 8Co0.2O2 cathode material based on Co-substituted α-Ni（OH）2 precursor

Co-substituted α-Ni（OH）2 was synthesized by a novel microwave homogeneous precipitation method in the presence of urea. LiNi0.8Co0.2O2 cathode material was synthesized by calcining Co-substituted α-Ni（OH）2 precursor and LiOH·H2O at 900℃for 10 h in flowing oxygen. XRD, FTIR, FESEM and electrochemical tests were used to study the physical and the electrochemical performances of the materials. The results show that the prepared LiNi0.8Co0.2O2 compound has a good layered hexagonal structure. Moreover, the LiNi0.8Co0.2O2cathode material demonstrates stable cyclability with a high initial specific discharge capacity of 183.9 mAh/g. The good electrochemical performance could be attributed to the uniform distribution of Ni^2＋ and Co^2＋ ions in the crystal structure and a minimal cation mixing in LiNi0.8Co0.2O2 host structure.     

Preparation and magnetic properties of CoFe2O4/TiO2 composite films

Using （Ti（OC4H9）4） and metal chlorates as starting materials, CoFe2O4/TiO2 composite films were prepared by sol-gel method. The effects of heat treatment temperature and pH of the precursor on microstructure and magnetic properties were studied. The phase structure of the samples was examined by X-ray diffraction. The microstructure was examined by scanning electron microscope, atomic force microscope and polarized microscope. The magnetic property was measured by vibrating sample magnetometer. The results show that the crystals of different phases grow up independently. CoFe2O4 is uniformly embedded into the TiO2 matrix in the prepared composite films, and the growth of composite films is dependent on the heat treatment temperatures and PH of the precursor. The average size of CoFe2O4 crystal is 19 nm in Nanocomposite film prepared when the heat treatment temperature is 800℃ and the pH of the precursor is between 2 and 3. The magnetism of the composite films is enhanced as the heat treatment temperature increases.     

F修饰对SiO2@TiO2亲疏水性及光催化性能的影响

采用两步法制备了氟修饰疏水性F-SiO_2@TiO_2材料.以三乙氧基氟硅烷(TEFS)为硅源,采用后嫁接的方法在短孔道MCM-41小球表面引入F原子,再利用醇热法在F-MCM-41小球表面生长TiO_2纳米晶颗粒.利用透射电子显微镜(TEM)、X射线粉末散射(XRD)、X射线光电子能谱(XPS)、N_2气吸脱附等手段表征了材料的物相组成和表面结构.研究表明:所制备的氟修饰F-SiO_2@TiO_2纳米复合材料为核壳结构,具有较大的比表面积、较好的介孔结构及较佳的热稳定性.同时,TiO_2纳米颗粒在F-MCM-41小球表面分散均匀、结晶度高、颗粒尺寸小且均一、与F-SiO_2结合牢固.重量吸附实验和光催化实验进一步证实F修饰可抑制水的吸附有利于提高F-SiO_2@TiO_2材料的疏水性和对气相有机污染物的光催化性能.     

三价铁离子掺杂对钛酸锂结构和化学性能的影响

采用溶胶凝胶法制备Li4-x/3FexTi5-2x/3O12(x=0,0.03,0.06,0.09)粉体活性材料,并优化了最佳掺杂量为x=0.03。通过X射线衍射(XRD)、扫描电镜(SEM)、恒流充放电测试对材料进行结构、形貌及电化学性能表征。结果表明:掺杂适量的铁离子不会改变钛酸锂的尖晶石结构和形貌。1C时,Li3.99Fe0.03Ti4.98O12首次放电比容量为145.40 m A·h/g;纯相的首次放电比容量仅为116.95 m A·h/g。     

Pu(H2O)53+和Pu(H2O)54+ 团簇的相对论密度泛函研究

用TPSSTPSS密度泛函方法, Pu离子和H₂O分子分别采用相对论有效原子实势(RECP)和6-31g基组, 研究了Pu(H₂O)₅³⁺和Pu(H₂O)₅⁴⁺ 团簇溶剂化和非溶剂化效应中的几何结构及紫外可见吸收光谱. 计算结果表明: 水溶剂环境对Pu(H₂O)₅³⁺及Pu(H₂O)₅⁴⁺ 团簇的几何结构影响都比较明显. NBO电荷分析表明水分子与钚离子之间没有直接的电荷转移. 所研究团簇的未配对电子都占据5f轨道. 在气相及水溶剂环境下, 所研究团簇的紫外可见吸收光谱存在较大差距. 主要的吸收峰大都源于f电子之间的跃迁.     

Mn_2O_3/CRF复合材料的制备及其在超级电容器中的应用

通过采用沉淀法在碳气凝胶表面负载金属氧化物三氧化二锰,制备得到Mn_2O_3/CRF复合材料。采用X射线衍射及电镜扫描等技术对所制备的复合材料进行结构形貌表征。实验结果发现碳气凝胶具有多重片层结构且孔隙发达。通过调节锰盐的含量考察三氧化二锰负载量对复合材料电化学性能的影响作用。采用循环伏安法及充放电测试对材料的电化学性能进行测试,结果表明Mn_2O_3/CRF复合材料具有良好的电容性及较好的可逆性。当Mn_2O_3含量达15%时复合材料的比电容最大,可达118.5 F/g。通过充放电测试1000次后发现该电极的比电容依然能够保持在一稳定值上,具有较好的稳定性。     

不同形貌LaBO_3型钙钛矿的制备及其催化H_2O_2分解反应性能

采用柠檬酸络合法制备了La BO3(B=Fe,Co,Ni)钙钛矿催化剂,通过X-射线粉末衍射(XRD)、傅立叶-红外光谱(FT-IR)、透射电镜(TEM)、X-射线光电子能谱(XPS)等对催化剂进行了表征,在室温下测定了其对H2O2的催化分解能力.结果表明:催化分解能力依次为La Ni O3>La Co O3>La Fe O3,说明Ni较Co和Fe能更好地分解H2O2.通过改变La Fe O3催化剂的形貌也能提高催化剂性能,如多孔状La Fe O3较负载在SBA-15上的La Fe O3具有更好的催化分解活性.     

Al2O3/WO3/ZrO2催化剂的制备及在酯交换反应中的研究

以松木为模板,采用模板法将不同含量的Al₂O₃添加到WO₃/ZrO₂复合氧化物中,采用X射线衍射、BET比表面积分析、拉曼光谱和NH₃等温吸附测试等手段对其进行表征,以评估其改进结果。将Al₂O₃/WO₃/ZrO₂催化剂应用到甲醇与乌桕油（非食用油）的酯交换反应中,在其他反应条件相同,Al₂O₃质量分数为3%时,生物柴油最高产率达到83.1%。结果表明：添加Al₂O₃稳定了ZrO₂的四方相结构,使得催化剂比表面积更大、孔数量增加;模板法制备的催化剂孔径分布均匀,WO₃呈高度分散无定型状态;引入Al₂O₃增加了WO₃/ZrO₂催化剂的中强酸性,对弱酸性和强酸性无明显改变。     

中温SOFC阴极材料La0.7Sr0.3Co1-xCuxO3-δ的制备及性能

采用固相反应法制备了La_0.7Sr_0.3Co_1-xCu_xO_3-δ系列中温固体氧化物燃料电池（SOFC）阴极材料粉体.对其进行晶体结构表征,高温电导率和热膨胀曲线测试,并选取其中性能较好的样品进行了单电池实验.结果表明,Cu的掺杂降低了（La,Sr）CoO La₃体系阴极材料的热膨胀系数,在x=0.05时电导率略高于未掺Cu的样品.以La_0.7Sr_0.3Co_0.95Cu _0.05O _3-δ为阴极、Ce_0.8Sm_0.2O_1.9为电解质组成的SOFC单电池,在850℃最大短路电流密度达511mA/cm²,最大输出功率密度约为0.106W/cm².     

聚苯胺/钛酸纳米复合材料的合成及其电化学和可见光催化性能的研究与应用

聚苯胺(PANI)/钛酸(H_2Ti_4O_9)层状纳米复合材料以苯胺(ANI)/H_2Ti_4O_9为前驱体,通过原位聚合的方法合成。复合材料的合成过程、形貌和结构通过XRD、SEM、IR和TGA/DSC表征手段进行研究。苯胺以单层且苯环垂直于层板的方式排列在H_2Ti_4O_9层间,聚合后的聚苯胺分子以单层方式排列在层间。PANI/H_2Ti_4O_9复合材料具有优异的热稳定性、氧化还原活性以及可见光催化降解亚甲基蓝活性,在电化学传感器和污水处理方面具有潜在的应用前景。     

基于植酸锆/普鲁士蓝复合膜的电催化行为研究

通过层层自组装技术,构建植酸锆/普鲁士蓝(Zr-IP_6/PB)多层结构膜.基于普鲁士蓝(PB)对双氧水(H_2O_2)有很高的电催化性能,加之5层植酸锆/普鲁士蓝膜多孔结构有利于传质过程,该H_2O_2传感器具有高灵敏度和高选择性.实验结果显示:修饰电极对H_2O_2响应的物质的量浓度范围为2.00×10~(-5)～1.76×10~(-3) mol·L~(-1),线性相关系数R=0.998 9.     

Fe3O4@NiSiO3纳米催化剂制备及催化臭氧化降解对苯二甲酸性能研究

采用水热法和溶胶凝胶法制备Fe₃O₄@SiO₂纳米颗粒,经表面镍刻蚀得到Fe₃O₄@NiSiO₃磁性纳米催化剂。利用XRD、TEM和VSM等手段表征催化剂的晶体和表面结构。构建类均相催化臭氧化体系,考察其催化降解对苯二甲酸性能。结果表明：在臭氧通入量10.52 mg.min_-1、催化剂投加量40 mg.L_-1和初始溶液pH=9的条件下,催化臭氧化反应20 min时对苯二甲酸降解率为78.13%,TOC去除率27.25%;5次循环实验后,PTA降解率仅下降2.75%。     

水热体系下二氧化钛与氧化石墨烯复合纳米晶的合成

 200 ℃下四方结构的二氧化钛(TiO2)与氧化石墨烯(GO)复合纳米晶在一个装有适量钛酸四丁酯、无水乙醇、氧化石墨烯和蒸馏水的密闭的水热釜中加热12 h后被制备。X射线粉末衍射仪（XRD)、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等一系列分析仪器被运用来揭示二氧化钛与氧化石墨烯复合纳米晶是由粒径大约160 nm的四方结构的二氧化钛纳米晶与氧化石墨烯复合而成,通过紫外吸收对其光学性能进行了必要的测试。
     

Relationship between luminescence and matrices in the system A12O3-B2O3-Ce2O3

The system Al₂O₃-B₂O₃-Ce₂O₃, with Al/B ratio varying from 4.5 to 2 and Ce/(Al+B) = 0.02, has been prepared at the temperature from 1 200 to 1 400°C. Relationship between luminescence and matrices in the system Al₂O₃-B₂O₃-Ce₂O₃ was investigated. It was found that some changes of the matrices occurred with Al/B ratio varying from 4.5 to 2. These results lead to a great change in luminescence properties, indicating variation of Ce-surroundings of crystal field. With the decrease of the ratio from 3 to 2, the excitation and emission peaks shift to shorter wavelengths. It was also found that a new type of rare earth luminescent materials was obtained with appropriate Al/B ratio.     

Preparation and photocatalytic activity of Cu-doped TiO2/SiO2

Cu²⁺-doped nanostructured TiO₂-coated SiO₂ (TiO₂/SiO₂) particles were prepared by the layer-by-layer assembly technique and their photocatalytic property was studied. TiO₂ colloids were synthesized by the sol-gel method using TiOSO₄ as a precursor. The experimental results showed that TiO₂ nanopowders on the surface of SiO₂ particles were well distributed and compact. The amount of TiO₂ increased with the increase in coating layers. The shell structure appeared to be composed of anatase titania nanocrystals at 550°C. The 2-layer coated TiO₂ particles on the surface showed a higher degradation rate compared with all the different-layer samples. The photocatalytic activity of Cu²⁺-doped TiO₂/SiO₂ was higher than that of undoped TiO₂/SiO₂. The optimum dopant content was about 0.10wt%.     

PbZr0.52Ti0.48O3的高压合成

研究使用2种原料进行PbZr_0.52Ti_0.48O₃的高压合成. 实验结果表明, 以PbO,ZrO₂和TiO₂(1:0.52∶0.48)为原料, 在1.5 GPa和3.6 GPa压力, 880~1 061 ℃条件下主要形成PbTiO₃, ZrO₂和Pb三相混合物, 仅在880 ℃附近有少量锆钛酸铅(PZT)相生成. 以Zr_0.52Ti_0.48O₂为B位先驱体, 与PbO混合后进行高压高温合成, 在1.5 GPa, 710~812 ℃条件下形成PbZr_0.52Ti_0.48O₃相, 未发现PbTiO3相. 对高压高温（1.5 GPa, 812 ℃）合成的PbZr_0.52Ti_0.48O₃样品进行变温拉曼测量, 在245 ℃时, 未发生结构相变; 在420 ℃时, 拉曼谱只有177.5,257.7,517 cm^-13个峰, 其结构由铁电相转变为立方顺电相, 因此高压合成的PbZr_0.52Ti_0.48O₃居里温度在420 ℃以下.      

NMR studies of the interaction betweenBacillis subtilis neutral proteinase and inorganic metal compounds

The interaction betweenBacillis subtilis neutral proteinase (B.S.NP) and inorganic metal compounds (CoCl₂, NiCl₂) was investigated by¹H NMR spectroscopy. It has been shown that the Zn(II) ion in the active center of the native enzyme may directly interact with external CoCl₂ and NiCl₂, producing Co(II)- and Ni(II)-substituted derivatives, and their¹H NMR spectra were obtained for the first time. From the¹H NMR spectra, the coordinated structure of the active center in the native enzyme was described.     

纳米Fe2O3-Al2O3复合材料的制备

采用溶胶-凝胶表面包覆法制备了纳米Fe₂O₃-Al₂ O₃复合材料, 利用X射线衍射和透射电镜对样品的物相、 粒度和形貌进行了研 究. 结果表明, α-Fe₂O₃掺杂降低了Al₂O₃相变温度, 在900 ℃可以得到稳定的α-Al₂O₃相.     

Hydrothermal synthesis, characterization and nonlinear optical effect of orthorhombic phase Ca2B6O11 · H2O

Hydrothermal treatment of calcium oxide and boric acid mixtures at temperatures between 234 °C and 300 °C has produced a colorless, transparent, orthorhombic compound Ca₂B₆O₁₁ · H₂O. Of the seven known members of the series of hydrated dicalcium hexaborate containing boron-oxygen six-membered ring anionic group (B₃O₈)^-7, only the title compound has been found to have the nonlinear optical effect. The second harmanic generation (SHG) effect of its crystal is larger than that of KH₂PO₄ (KDP). The reflection spectrum has shown that this compound has no absorption in the experimental wavelength range (800–240 nm). Its crystal structure is favorable for generating the nonlinear optical effect.