Pt和Al2O3改性SO4^2-/ZrO2正己烷异构化反应性能

在保持其他制备条件,如pH、干燥条件、焙烧温度、Pt的浸渍条件以及Al2O3和Pt的含量相同的情况下,通过Al的不同引入方法,即共沉淀法(CP)、成型法(SH)、悬浮法(SU)和混和法(MI),制备了4种Pt-SO42-/ZrO2-Al2O3(PSZA)催化剂。使用N2吸附和微库仑仪分析了催化剂的组织结构和硫含量。分别使用X射线光散射仪(XRD)、H2程序升温还原(TPR)及NH3程序升温解析(TPD)研究了催化剂的晶相结构、氧化还原性质和表面酸性质。在固定床反应器上考察了反应温度对催化剂正己烷异构化反应的影响和异构化产物分布。成型法催化剂仅探测到四方晶相,表明该种Al的引入方法延缓了四方相转为单斜相;并且成型法催化剂具有一个强的最低的TPR还原峰温度,表明Al的成型引入法增强了硫的还原。催化考评结果表明成型法催化剂具有最高的催化性能。催化剂的物化表征结果表明了催化活性同催化剂的氧化还原性质关联较好,而同硫含量、酸强度及强酸位数量关联性不好。实验结果表明Al的引入方式对于PSZA催化剂在正己烷异构化中具有高催化活性非常关键。     

CO2气氛下纳米铬铈复合氧化物乙苯脱氢行为的研究

利用共沉淀法制备了纳米级的铬铈复合氧化物,研究了这些催化剂在CO2气氛下对乙苯的氧化脱氢。结果发现,复合氧化物的催化活性明显高于单纯的氧化物,这可能与复合氧化物中含有较多量的Cr^6 以及Ce^4 容易还原为Ce^3 有关,与纯N2气氛相比,CO2对乙苯反应具有明显的促进作用。     

一种新的三维MDCT的快速算法

提出了计算三维改进的离散余弦变换(MDCT)的一种快速方法,可以有效减小数据量,提高计算机存储和运算的效率.首先将序列长度为N1×N2×N3的三维MDCT转化为(N1/2)×(N2/2)×(N3/2)的三维离散余弦变换Ⅳ型(DCT-Ⅳ)(N1=2m1,N2=2m2,N3=2m3),然后将后者转化为8个长度为(N1/4)×(N2/4)×(N3/4)的三维离散余弦变换Ⅱ型(DCT-Ⅱ),最后再通过变量代换和加法运算实现整个快速计算过程.同时,通过编写程序验证算法的正确性,并分析该算法的计算复杂度.结果表明:较之传统的行列方法,所提出的算法能够有效使计算复杂度降低75%左右,实现了计算机在三维信号处理领域的运行速率的提高.     

Tunable and enhanced luminescence of Ba2−xCaxSiO4−yN2/3y:Eu2+ phosphors for white light-emitting diodes

Color tuning and luminescence enhancement are predominant challenges for improving the performance of white light emitting diodes(LEDs) toward commercial application. In this paper, a novel promising Ba_(2-x)Ca_xSiO_(4-y)N_(2/3y):Eu~(2+) tphosphors with tunable and enhanced luminescence for phosphors converted LEDs(pc-LEDs) have been successfully synthesized by a direct gas-reduction nitridation method. The effects of Ca and N doping on the phase purity, morphology and optical properties of Ba_(2-x)Ca_xSiO_(4-y)N_(2/3y):Eu~(2+) tphosphors were also systematically investigated. The optical results show that Ba_(2-x)Ca_xSiO_(4-y)N_(2/3y):Eu~(2+) tphosphors can be actively excited over a broad range from 250 to430 nm. With the adding of different concentrations of Ca~(2+) tions in phosphors, the emission color wavelength can be tailored from 501 to 441 nm by a 375 nm NUV LED excitation source. Furthermore, it has been found that the emission and absorption of Ba_(2-x)Ca_xSiO_(4-y)N_(2/3y) tphosphor can be significantly improved when N~(3-) ions were introduced into the host lattices. The intensity of Ba_(1.5)Ca_(0.5)SiO_(4-y)N_(2/3y):Eu~(2+) tphosphor was 3.4 times higher than the phosphor without N doping. The fabrication and characterization of pc-LEDs using Ba_(2-x)Ca_xSiO_(4-y)N_(2/3y):Eu~(2+) tphosphors-silica gel as the coating layer onto 375 nm-emitting In Ga N LED caps demonstrated the superior optical and current tolerant properties,making it a promising and competitive candidate for commercial utilization in white LED applications.     

离子交换均匀沉淀法合成纳米CeO 2研究

以Ce(NO3)3.6H2O、Na2CO3为原料,采用新型弱酸性阳离子交换树脂均匀沉淀法制备CeO2前驱体,经500℃焙烧1～4h后获得了高纯度的纳米CeO2晶体.用热重分析、X射线衍射、扫描和透射电子显微镜等对前驱体和样品的形貌和粒径分布进行了表征,并对涉及的均匀沉淀机理进行了探讨.结果表明,制备的CeO2纳米晶体属立方晶系,样品分散性好,平均粒径为30～50nm.离子交换树脂均匀沉淀法具有操作简单易行,成本低,同时避免使用有机溶剂和表面活性剂,污染小,后处理容易,离子交换树脂可再生重复使用等优点.     

稀土掺杂TiO2纳米微粒的合成、表征及光催化活性

采用溶胶-凝胶法制备纯的及掺杂不同量铈的TiO2纳米粒子,利用UV-Vis漫反射光谱及XRD等对所制备样品进行表征.以高压汞灯为光源、甲基橙水溶液的脱色为模型反应,研究了CeO2/TiO2的光催化降解反应活性.实验发现: 掺杂Ce的TiO2纳米粒子反射光谱特性向可见光方向红移到500.nm,比纯的TiO2纳米粒子对光的吸收率高、吸收能力强;掺杂的Ce4 仅有少量进入TiO2晶格中,大部分的Ce4 是以小团簇的CeO2形态均匀地分散在TiO2纳米粒子中或者是覆盖在其表面上.说明掺杂Ce能提高TiO2光催化反应活性,且掺杂Ce摩尔分数最佳值为2.0%.     

Suitable energy platform significantly improves charge separation of g-C_3N_4 for CO_2 reduction and pollutant oxidation under visible-light

The photocatalytic activities of g-C_3N_4 can be significantly improved by increasing life time of the photogenerated charges. Here, in this work we introduced TiO_2 as proper energy platform to accept the photogenerated electrons from g-C_3N_4 during photocatalysis. The nanophotocatalysts formed from the combination of a suitable amount of TiO_2 nanoparticles and g-C_3N_4 nanosheets showed 8.75 and 4.22% enhancement in photocatalytic activities for CO_2 reduction and 2-chlorophenol(2-CP) degradation under visible light illumination as compared to bare g-C_3N_4. Based on the surface photovoltage spectra, photoluminescence spectra and examination of formed hydroxyl radicals, it was confirmed that these enhanced photoactivities were attributed to the much-improved charge separation via the electron transfer from g-C_3N_4 to TiO_2. From trapping experiments,it was found that hydroxyl radicals were the major species involved in the photocatalytic degradation of 2-CP.This study is helpful to synthesize efficient photocatalysts to cope with energy and environmental issues.     

稀土CeO2纳米固溶体粉末晶格常数与成分的关系

氧化物的晶格常数是材料研究和运用的一个重要参数. 从理论上预测氧化物固溶体的晶格常数是物理学家和材料学家从理论上研究物性参数的方法之一. 经研究, 推导出了计算立方CeO₂ 纳米固溶体晶格常数与固溶体成分关系的方程. 将理论计算纳米氧化物固溶体的晶格常数的方程用于CeO₂ - ZrO₂, CeO₂ - Bi₂O₃ , CeO₂ - La₂O₃, CeO₂ - ZrO₂ - ThO₂ 纳米固溶体晶格常数的计算, 发现晶格常数随固溶体成分变化与立方CeO₂纳米固溶体晶格常数实验结果基本一致, 误差不大于0. 3% , 1. 7%, 3. 4%, 0. 4%.     

三种新型氮化锗材料的第一原理原子尺度研究

采用第一原理框架下的平面波+赝势方法,对Ge_3N_4的三种新结构进行了计算.计算结果表明四方、单斜和正交结构的氮化锗满足力学和热力学稳定条件,都可以稳定存在.o-Ge_3N_4的抗剪切能力和硬度都是三者之中最高的.本文得到了三种相的声子谱,即介电函数、能量损失谱和光吸收谱;研究发现在可见光区域三相的吸收都很弱,主要呈现出紫外吸收特征.介电函数虚部的峰值是由N-2p轨道的电子向Ge-4s和4p轨道跃迁形成的.声子谱表现出N原子和Ge原子杂化的特征.此外,也成功地得到了静态介电常数和离子体频率.     

Binder-free heterostructure(g-C_3N_4/PPy) based thin film on semi-flexible nickel foam via hybrid spray technique for energy storage application

A semi-flexible binder-free graphitic carbon nitride(g-C_3N_4) intercalated polypyrrole(PPy) nanocomposite thin film was prepared via hybrid electrospray technique. A homogeneous thin film was achieved by the controlled spray process. A deposited thin film illustrated the amorphous nature of composite with high surface purity and good chemical composition. The surface analysis confirmed the smoother surface with well-defined distinct phases of g-C_3N_4 and PPy matrix in the composite thin film. The electrochemical studies exhibited that a maximum areal capacity of the thin film was achieved to be 289.6 mF/cm~2 at a current density of 0.4 mA/cm~2,which is higher than that of pristine PPy(194.8 mF/cm~2). The heterostructure electrode illustrated that the life cycles of 99% could be up to 10,000 cycles with low resistance due to the synergetic effect of g-C_3N_4 and PPy matrix with strong material adhesion(hybrid spray process) on the surface. A binder-free heterostructure thin film will play a significant role in the energy storage application.     

Preparation and Characterization of TiO_2 Nanotubes Decorated by CuO and CeO_2 Particles

A novel catalyst, TiO_2 nanotubes(TiO_2 NTs) composite decorated by CuO and CeO_2 particles, was prepared by a simple and cost-effective method. The TiO_2 NTs were fabricated by the hydrothermal method, and CuO and CeO_2 particles loaded onto TiO_2 NTs(CuO/CeO_2@TiO_2 NTs) were prepared by the water bath heating method. The CuO/CeO_2@TiO_2 NTs were investigated and characterized by transmission electron microscope(TEM), energy dispersive spectrometer(EDS), photoluminescence(PL), X-ray diffractometer(XRD) and ultraviolet-visible light diffuse reflectance spectrum(UV-Vis DRS). Both the p-n heterojunction formed at the p-CuO and n-TiO_2 interfaces and the highly induced electron transfer of CeO_2 can greatly promote the separation of electrons-holes. Therefore, CuO/CeO_2@TiO_2 NTs show enhanced absorption and have potential applications in photocatalysis.     

Nd、Ce掺杂BaTiO3基陶瓷的研制及介电性能研究

本文采用固相法,分别用CeO2和Nd2O3掺杂钛酸钡基陶瓷,对其实验前后进行对比和物相分析,探讨了掺杂比例对其介电性能影响的规律.当w(CeO2)为0.4%时相对介电常数最大(79899),当w(CeO2)为1%时介质损耗最小(0.0223);当Nd摩尔含量为3‰时相对介电常数最大(31309),当Nd摩尔含量为1.5‰时介质损耗最小(0.0457).同时用X衍射法分析了粉体预烧前后的晶相变化和最佳掺杂比例时粉体的晶相变化.在适当条件预烧处理有助于介温谱的变化,介温特性得到改善.本文对所用的掺杂方法的可行性进行了分析.     

活性钎料钎接Si_3N_4陶瓷的机理研究

通过钎料中常用活性材料与被钎陶瓷Ｓｉ＿３Ｎ＿４之间的物理现象和化学反应，讨论了活性材料所起的作用，即通过活性金属与Ｓｉ＿３Ｎ＿４陶瓷的化学反应形成反应过渡层而结合，同时活性材料改善了钎料在Ｓｉ＿３Ｎ＿４陶瓷表面的漫流性能．但因为反应产物与Ｓｉ＿３Ｎ＿４陶瓷热物理性能相差较大，故活性材料的加入量应限制在一定范围以内。用Ａｇ－Ｃｕ－Ｔｉ钎料钎接Ｓｉ＿３Ｎ＿４／钢时，在Ｓｉ＿３Ｎ＿４／钎料过渡区生成了富ＴｉＮ层和富Ｔｉ＿３Ｓｉ＿５层，控制这两个反应结合层的成分和厚度可能是提高钎接接头强度的关键之一。此外在一定范围内增加钎料层厚度时，钎接接头强度有明显提高。     

Effect of CeO_2 on heat transfer and crystallization behavior of rare earth alloy steel mold fluxes

To improve the heat transfer capability and the crystallization property of the traditional mold flux, CaF_2 was replaced with B_2O_3. Then, the influences of CeO_2 on the heat transfer and the crystallization of the CaF_2-bearing mold flux and the new mold flux with 10 wt% B_2O_3 were studied using a slag film heat flux simulator and X-ray diffraction(XRD). The results revealed that the addition of CeO2 reduced the heat transfer by increasing the solid slag thickness and the crystallization of two mold fluxes. However, CeO_2 had less effect on the B_2O_3-containing mold flux compared with the CaF_2-bearing mold flux. According to the analyses, the CeO_2 contents in the CaF_2-bearing mold flux and the B_2O_3-containing mold flux should not exceed 8 wt% and 12 wt%, respectively. Therefore, these experimental results are beneficial to improve and develop the mold flux for casting rare earth alloy steels.     

磨粒粒径对Si3N4结构陶瓷冲蚀磨损性能的影响

以冲蚀磨损工况下的典型应用材料Cr15Mo3高铬铸铁为对比材料,采用转盘式液-固双相流试验机研究了不同SiC磨粒粒径对Si3N4结构陶瓷抗冲蚀磨损性能的影响,分析了试验材料冲蚀磨损的微观失效机制.研究结果表明:在各种粒径磨粒的冲蚀磨损条件下,Cr15Mo3铸铁的冲蚀磨损率都比Si3N4结构陶瓷的高,Si3N4结构陶瓷的抗冲蚀磨损能力是Cr15Mo3铸铁的20倍左右;粗颗粒磨料冲蚀条件下试验材料的体积损失比细颗粒磨料冲蚀条件下的大,即磨粒越粗冲蚀磨损越严重;在微观上,Cr15Mo3的腐蚀坑、冲蚀坑多,基体材料冲刷磨损严重,W型失效形貌明显,而Si3N4结构陶瓷的冲蚀磨损面比较光滑,材料失效主要是晶界粘结相失去多所致;结构致密、晶粒细小并有细小柱状晶的存在等是Si3N4结构陶瓷抗冲蚀磨损性能优异的主要原因.     

原子团簇N8的分子模型设计与量子化学计算

根据N5^ 和N3^-两种离子的存在,预测可能存在原子团簇N8,使用分子模拟软件设计出20种N8的同分异构体,然后采用量子化学从头算方法在HF／STO-3G理论水平下对各个分子进行了全构型优化、热力学计算和谐振频率分析,最后讨论了N8的实验合成路线．计算结果表明,有12种同分异构体可稳定存在,其中平面双五元环结构(D2h)最为稳定,能量分析表明,可稳定存在结构的N8含有比4个N2高得多的能量,如果能够合成出N8,将会成为潜在的绿色高能量密度材料。     

电化学还原石墨烯用于水合肼的电催化氧化及检测

采用电化学还原技术制备了还原石墨烯.采用扫描电镜、Raman光谱、AFM等技术表征了石墨烯的形貌和结构特征.采用电化学测试技术研究了还原石墨烯修饰电极的电化学性能及对水合肼(N_2H_4·H_2O)的电催化氧化活性.结果表明,该石墨烯电极材料具有优异的电子传导性能.与裸玻碳电极相比,石墨烯修饰电极对水合肼表现出优异的电催化氧化活性.在最佳的实验条件下,将该石墨烯修饰电极用于水合肼的灵敏检测.在1×10~(-5)~1×10~(-4) mol/L范围内,氧化峰电流与水合肼的浓度呈良好的线性关系.该石墨烯修饰电极材料有望用于环境中水合肼等有机小分子的灵敏检测.     

CeO2包覆TiO2的XPS研究

利用光电子能谱ＸＰＳ研究ＣｅＯ２包覆ＴｉＯ２后氧化还原性能。ＴＥＭ照片证明实验中制备出包覆材料：Ｃｅ３ｄ谱线说明加入ＴｉＯ２后ＣｅＯ２非常容易还原,吸氧时它能够再氧化。     

一步法合成纳米CeO2溶胶及其分散稳定机理

针对胶溶法制备纳半分散体时条件严格、过程繁琐的问题,以硝酸过量的Ce(NO3)3溶液和氨水为反应物,在低pH值条件下,通过一步法合成了在水介质和乙酸乙酯介质中稳定分散的亮黄色透明的纳米CeO2胶体分散体;讨论了表面活性剂(DBS)用量与萃取率的关系,得出了用乙酸乙酯萃取时Ce(NO3)3溶液与DBS用量的最佳比.电镜照片观察到,CeO2纳米粒子在水介质和乙酸乙酯介质中均呈球形,粒径分布均匀,平均粒径约为3～5nm.初步研究探讨了在两种介质中稳定分散的机理.     

Solvent-free selective hydrogenation of o-chloronitrobenzene to o-chloroaniline over alumina supported Pt nanoparticles

A supported Pt/Al2O3 catalyst was prepared by immobilizing preformed colloidal Pt nanoparticles on Al2O3. The particle size and size distribution of Pt particles on Al2O3 remained the same as the colloidal nanoparticles. Selective hydrogenation of o-chloronitrobenzene to ochloroaniline was performed on the as-prepared Pt/Al2O3 nanocatalyst without using any solvent and 88.5% selectivity to o-chloroaniline at 98.2% conversion of o-chloronitrobenzene was achieved. Further catalytic experiments with metal cation modification showed that some metal cations could improve the activity in various degrees while maintaining the high selectivity. Especially, 99.8% selectivity to o-chloroaniline at ~100% conversion was attained with Sn4t.