Ni—Pb／C催化剂用于乙醇羰化反应失活机理的研究

利用电子探针能谱（ＥＤＳ）、扫描电子显微镜（ＳＥＭ）、Ｘ－射线衍射（ＸＲＤ）对Ｎｉ－Ｐｂ／Ｃ催化剂进行了表征。结果表明，在２５０℃下，催化剂使用１６０ｈ仍有高的活性，未发现有积炭现象。但在３００℃时，活性下降，收率降至３０％。在高温条件下，Ｐｂ富集在催化剂表面上，使Ｎｉ＾０活性中心数量减少，导致催化剂失活。当温度回复到２５０℃时，催化剂活性又慢慢地恢复。这种失活是可逆的。     

通过Bi3+发光特征判定“争议”格位——以Ca2MgSi2O7:Bi3+荧光粉为例

在以往的研究工作中,人们经常关注给定基质具有多个格位所对应多发光中心的光致发射。 取决于所掺杂的基质,多个格位的晶体化合物应该可以提供相应的多发光中心,但某些化合物有时只会表现一个发光中心,由此产生“争议性”发光中心。 据以往研究,以稀土离子掺杂而为人所知的经典镁黄长石(Ca₂MgSi₂O₇)长余辉化合物具有“争议性”Ca格位。 为此,在本文中以非稀土离子(Bi³⁺)特有的发光特性从侧面来研究Ca₂MgSi₂O₇化合物中的“争议性”Ca格位问题。 结果表明,在250和276 nm激发波长激发下,所有的Bi³⁺掺杂Ca₂MgSi₂O₇样品均有峰位位于582和350 nm的两个Bi³⁺特征发射带。结合晶体结构分析,光谱结果表明,Ca₂MgSi₂O₇:Bi³⁺荧光粉具有对应于六配位和八配位的两个不同Ca²⁺格位的两个Bi³⁺发光中心,即,Bi³⁺(Ⅰ)(~582 nm)和Bi³⁺(Ⅱ)(~350 nm)发光中心。 此外,光谱分析进一步表明,Bi³⁺(Ⅰ)与Bi³⁺(Ⅱ)具有单向的能量传递,而且,发现这两个发光中心所对应的相对发射强度是依赖于激发波长和Bi³⁺掺杂浓度。 实验证明了Ca₂MgSi₂O₇晶体化合物具有两个Ca格位,而不是有些工作中所讨论的一个Ca格位。 本文工作可以为已知或未知的具有“争议性”格位的晶体化合物的验证提供新的借鉴。     

基于Huber的高阶容积卡尔曼跟踪算法

为改善高阶容积卡尔曼滤波算法的滤波精度和鲁棒性, 提出了一种新的基于Huber的高阶容积卡尔曼滤波算法. 在采用统计线性回归模型近似非线性量测模型的基础上, 利用Huber M 估计算法实现状态的量测更新. 进一步结合高阶球面-径向容积准则的状态预测模块构成基于 Huber的高阶容积卡尔曼跟踪算法. 重点分析了Huber代价函数的调节因子对算法跟踪性能的影响. 通过对纯方位目标跟踪和再入飞行器跟踪两个实例验证了所提算法的跟踪性能优于传统高阶容积卡尔曼滤波算法.     

Wearable membranes from zirconium-oxo clusters cross-linked polymer networks for ultrafast chemical warfare agents decontamination

The urgent need for immediate personal protection against chemical warfare agents （CWAs） spurs the requirement on robust and highly efficient catalytic systems that can be conveniently integrated to wearable devices.Herein,as a new concept for CWA decontamination catalyst design,sub-nanoscale,catalytically active zirconium-oxo molecular clusters are covalently integrated in flexible polymer network as crosslinkers for the full exposure of catalytic sites as well as robust framework structures.Th...     

Vinyl polymerization of norbornene with nickel catalysts bearing [N,N] six-membered chelate ring: Important influence of ligand structure on activity

Norbornene polymerizations with nickel complexes bearing [N,N] six-membered chelate ring activated with methylaluminoxane were investigated. The influence of ligand structure such as β-diimine, β-diketiminate, fluorinated β-diketiminate, and anilido-imine ligand on catalytic activities for norbornene polymerization was evaluated in detail. Ligands led to different electrophilicity of the nickel metal center, and a relatively positive nickel metal center would result in high catalytic activities for norbornene polymerization. The influences of polymerization temperature and Al/Ni ratio on norbornene polymerization with nickel catalysts bearing β-diimine, β-diketiminate, and fluorinated β-diketiminate ligands were also examined. All of the obtained polymers catalyzed by these nickel catalysts bearing [N,N] ligand are vinylic addition polynorbornenes with different molecular weights.     

Laser-diode-excited intense luminescence and green-upconversion in erbium-doped bismuth-germanate-lead glasses

We investigate the spectroscopic properties of the 1.5-microm emission from the (4)I(13/2)-->(4)I(15/2) transition of Er(3+) ions in bismuth-germanate-lead glasses for applications in broadband fiber amplifiers. The emission peak locates at 1532nm with a full width at half-maximum (FWHM) of approximately 65nm. The measured lifetime and the calculated emission cross-section of this transition are 3.3ms and 8.66x10(-21)cm(2), respectively. IR-to-green-upconversion occurs simultaneously upon excitation of the 1.5-microm emission with a commercially available 980nm laser diode. Effects of PbF(2) content on the thermal stability, structure and spectroscopic properties of Er(3+)-doped bismuth-germanate-lead glasses have been examined. We find that the substitution with PbF(2) provides a couple of potentials: shortening the UV cutoff band and decreasing the phonon energy of host glasses. Codoping of Yb(3+) significantly enhances both the green-upconversion and 1.5-microm emission intensity by means of a nonradiative Yb(3+)-->Er(3+) energy transfer. Energy transfer processes and nonradiative phonon-assisted decays could account for the population of the (2)H(11/2) level, which is an emitting level of the green-upconversion of Er(3+). The results indicate the possibility towards the development of bismuth-germanate-lead based glasses as photonics devices.     

Platinum free ternary electrocatalysts prepared via organic colloidal method for oxygen reduction

Novel ternary palladium based alloy catalysts, PdFeIr/C, for oxygen reduction reaction (ORR) have been successfully prepared via an organic colloid method with ethylene glycol as solvent and sodium citrate as complexing agent. The catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX). Electrochemical activity of the catalysts for ORR was evaluated by steady state polarization measurements, which were carried out on an ultra thin layer rotating disk electrode (RDE). Compared to pure Pd/C and Pd₃Fe/C, results showed that the ORR activity of PdFeIr/C was highest, and its methanol tolerance was better than Pt/C catalyst.     

An electrochemical approach tunes the electric property of benzoylferrocene-modified supported lipid membrane

A benzoylferrocene (BFc) supported 3-sn-phosphatidylcholine (PC) film electrode was prepared by casting the solution of BFc and PC in chloroform onto the surface of platinum (Pt). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) results showed that BFc, retained in the biological membrane, acted as a shuttle for electron transfer across the supported bilayer lipid membranes (s-BLMs). Doping of BFc increased membrane conductivity, while electrochemical oxidation of BFc greatly changed the membrane conductivity, the membrane impedance characterized by charge transfer resistance (R_ct) dramatically increased about 400 times (from 10.32 to 3919.67 kΩ). Interestingly, the electrochemical oxidized BFc buried in the membranes could be reduced by applying a low potential, and this led to recurrent of a conductive membrane. The conductivity of the s-BLMs could be controlled by the redox status of embedded BFc molecules. The approach provided a facile and novel way to electrochemically control the membrane conductance of s-BLMs by embedding BFc as a switchable redox mediator.     

Preparation and performance analysis of PE-supported P(AN-co-MMA) gel polymer electrolyte for lithium ion battery application

Copolymer, poly(acrylonitrile-co-methyl methacrylate) (P(AN-co-MMA)), was synthesized by solution polymerization with different mole ratios of monomers, acrylonitrile (AN) and methyl methacrylate (MMA). Polyethylene (PE) supported copolymer and gel polymer electrolyte (GPE) were prepared with this copolymer and their performances were characterized with FTIR, TGA, SEM, and electrochemical methods. It is found that the GPE using the PE-supported copolymer with AN to MMA = 4:1 (mole) exhibits an ionic conductivity of 2.06 × 10⁻³ S cm⁻¹ at room temperature. The copolymer is stable up to 270 °C. The PE-supported copolymer shows a cross-linked porous structure and has 150 wt% of electrolyte uptake. The GPE is compatible with anode and cathode of lithium ion battery at high voltage and its electrochemical window is 5.5 V (vs. Li/Li⁺). With the application of the PE-supported GPE in lithium ion battery, the battery shows its good rate and initial discharge capacity and cyclic stability.