Li NMR, ionic conductivity and self-diffusion coefficients of lithium ion and solvent of plasticized organic-inorganic hybrid electrolyte based on PPG-PEG-PPG diamine and alkoxysilanes

Organic-inorganic hybrid electrolytes based on poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (D2000) complexed with LiClO₄ via the co-condensation of an epoxy trialkoxysilane and tetraethoxysilane have been prepared and plasticized by a solution of ethylene carbonate (EC)/propylene carbonate (PC) mixture (1:1 by weight). The cross-linked hybrid network shows no solvent exudation and retains a large amount of plasticizer over 70 wt.% in stable state. The in situ built in silica network provides the hybrid electrolytes with good mechanical properties. The ionic conductivity of the dry hybrid electrolyte films was enhanced by two orders of magnitude via plasticization, reaching a maximum conductivity value of 4.0 × 10⁻³ S/cm at 30 °C. Variable temperature ⁷Li-{¹H} magic angle spinning (MAS) NMR demonstrated that the Li⁺ cations can be complexed by the polymer network as well as by the plasticizing solvents, but not with the incorporated silica network. Furthermore, the ⁷Li chemical shift change indicated a progressive change in the lithium coordination from lithium-polymer to lithium-solvent with increasing temperatures. The role of the solvents and the mobility of the lithium ions were investigated by pulsed gradient spin echo (PGSE) NMR measurements to elucidate the behavior of the ionic conductivity.     

微/纳米ZnO绒球的制备及对混合污水的光降解

以自制的谷氨酸-氟硼酸(GluBF4)离子液体水溶液为反应介质,以物质的量比为1∶6的二水合醋酸锌[Zn(Ac)2·2H2O]和NaOH为原料,室温(25℃,20min)制备前驱体,再微波辅助加热(80℃,10min)制备了纳米氧化锌粉体,获得了纳米结构微米尺寸ZnO绒球。利用场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)、比表面积(BET)、能谱(EDS)等对产物进行了表征。结果表明,所得产物为六方晶系纤锌矿结构,粉体粒径20.4nm,绒球比表面积为27.6m2/g。该纳米材料具有较高的光催化降解有机污染物活性。以紫外光为光源,50 mg微/纳米ZnO绒球为光降解催化剂,取500mL北京雪莲羊绒股份有限公司排污口混合印染污水进行光降解实验,在30min内光降解效率达到了100%,催化剂可回收重复利用,并对光降解机理进行了初步分析。     

Development of sodium hybrid quasi-solid electrolytes based on porous NASICON and ionic liquids

Lithium-ion batteries are currently the alternative of choice to overcome the increasing demand of energy. However, besides the scarcity of lithium and limited geolocation, it is believed that such batteries have already reached their maximum maturity. Sodium batteries emerge as an alternative to produce the new, so called, post-lithium batteries. In this study, we explore (i) the effect of sodium content and sintering temperature in solid electrolytes based in NASICON-type compounds and (ii) the use of two methodologies to obtain porous NASICON samples: application of natural substances and organic materials as pore-formers and freeze casting. The main purpose is the attainment of hybrid quasi-solid state electrolytes, with enhanced room temperature conductivity, based on porous ceramic electrolyte layers infiltrated with ionic liquids. Using this approach, porous samples with different microstructure and porous morphology and distribution were achieved, providing an enhancement in conductivity (ranging from 0.45 to 0.96 mS cm⁻¹ at 30 °C) of one order of magnitude for infiltrated samples respect to pore-free samples. According to these results the porous NASICON might be considered as a functional macroporous inorganic separator that can act as a Na⁺ reservoir.     

不锈钢加铁稀土离子硫氮碳共渗工艺的研究

对1Cr18Ni12Mo2Ti奥氏体不锈钢在稀土催渗条件下进行了加与未加辅助铁板的离子硫氮共渗对比试验.试验表明:稀土具有很强的催渗作用.在与辅助铁板的共同作用下,可使奥氏体不锈钢的氮化温度降低60℃,减小了零件的变形;在相同的共渗温度条件下,可使氮化层深度比离子硫氮碳共渗增加30%以上,比未加辅助铁板的稀土离子硫氮碳增加10%.且稀土元素可渗入钢表层,细化渗层组织,促进氮碳化合物弥散细小析出,提高渗层硬度.     

碳钢表面离子镍铬共渗的研究

本文主要介绍了碳钢双层辉光离子镍铬共渗的试验结果,探讨了渗层厚度与镍铬共渗工艺参数的关系。试验表明,镍铬共渗层厚度取决于共渗温度、保温时间和试样材料,其变动范围0～300μm,共渗层中的镍铬含量可在0～90%的范围内变动。此外,还列举了双层辉光离子镍铬共渗工艺在碳钢钢板及碳钢零件上的应用。     

基团立体屏蔽效应对取代咪唑离子液体酸性的影响

影响取代咪唑阳离子C2-H酸性(pKa)的重要因素有二:H原子所带的部分正电荷和取代基的立体屏蔽效应,前者可用C2-H的1H NMR化学位移δC2-H度量,后者用基团拓扑立体效应指数TSEI衡量.咪唑阳离子C2-H的pKa可由以下方程估算:pKa=58.10-4.208δC2-H+1.659TSEI该式的标准偏差只有0.28 pKa单位,估算结果与文献报导的pKa值相吻合.表明如要精确估算pKa,必须考虑取代基立体屏蔽效应;当希望用碱性较低的亲核试剂脱除取代咪唑阳离子的C2-H形成卡宾时,应采用芳香基取代的咪唑离子;若使用取代咪唑离子液体作溶剂,并且在碱性较强的条件下进行有机反应,则最好选择立体屏蔽效应大的非芳香基取代的咪唑离子.     

Preparation and performance of IPMC actuators with electrospun Nafion-MWNT composite electrodes

A new ionic polymer actuator was prepared with Nafion^®-117 membrane and electrodes made of an electrospun Nafion^®/multiwalled carbon nanotube (MWNT) web. The surfaces of composite electrodes were ion-beam coated with gold layers of 2-3 μm thickness to reduce the surface resistance. The composite electrodes offer several advantages over conventional platinum electrodes prepared via electroless plating process, i.e. flexibility, simple processability in large scales, and batch-to-batch reproducibility. The new ionic polymer-metal composite (IPMC) actuators showed a rapid and large bending motion. Under an applied potential of 3 V dc, the maximum horizontal displacement (δ_max) measured at the tip of IPMC strip (cantilever length: 20 mm) was 16.7 mm, the tip velocity in the initial linear region was 10.5 mm/s, 88% of the δ_max was reached within initial 5 s, and the generated strain% was 0.79 (13.6 mm, 7.2 mm/s, 85%, and 0.88, respectively for a conventional Nafion^®-IPMC made via the electroless plating of platinum). It was noted that the energy efficiency of strain was over 10 times higher than that of the conventional Nafion^®-IPMC. And the crack formation of metal electrode after repeated bending deformation significantly reduced with the introduction of relatively flexible electrode assembly into the IPMC architecture. The remarkable improvements in its performance were considered to be due to the efficient quantum chemical and double-layer electrostatic effects in a charge injection model, induced by the good dispersion of MWNTs through a typical electrospinning technique.     

Amperometric biosensor for catechol using electrochemical template process

A novel amperometric biosensor for the determination of catechol was developed accordingly to the electrochemical template procedure. The optimum fabricating conditions of the biosensor were studied. The resulting biosensor with the limit of less than 0.05 μM can be used for detection of catechol in the linear range of 2.5-140 μM. The maximum response current (I_max) and the Michaelis-Menten constant (k′_m) are 3.08 μA and 77.52 μM, respectively. The activation energy (E_a) of the polyphenol oxidase (PPO) catalytic reaction is 25.56 kJ mol⁻¹ in the B-R buffer. The stability of the PANI-CA biosensor fabricated with the electrochemical template process (retains 86% of the original activity after four months) is much higher than that fabricated with one-step and two-step processes (retains 75% of the original activity after four months). The effects of potential and pH on the response current of the biosensor are also described.     

Recovery of magnetic ionic liquid [bmim]FeCl<Subscript>4</Subscript> using electromagnet

Recovery of 1-butyl-3-methylimidazolium tetrachloroferrate ([bmim]FeCl₄) from its mixture with water was investigated. The [bmim]FeCl₄ rich phase in the mixture forming two-phase was successfully separated, while homogeneous mixtures could not be separated. However, the concentration of the homogeneous mixture varied as a function of the magnetic field strength. Therefore, a combination of magnetic field and conventional methods to recover magnetic ILs from reaction mixtures will be very useful and have great potential.     

Selenium Speciation Studies from Soan-Sakesar Valley,Salt Range,Pakistan

Abstract

A regional study of Selenium (Se) speciation in surface waters, groundwaters, and saturation extracts from Soan-Sakesar valley Salt-Range, Pakistan was started in March 1994 and completed in October 1996. Groundwaters, streams, and springs had median concentrations of: total Se 48, 404.5, and 82 μg/l; Se^+VI 40, 350 and 51 μg/l; Se^+IV 8, 48 and 29 μg/l; Se^-II 0, 6.5 and 2.0 μg/l, respectively. The concentration of Se exceeded the recommended water quality guidelines for drinking and irrigation water of 10 and 20 μg/l, respectively. In saturation extracts, median total Se, Se^+VI, Se^+IV and Se^-II were 190, 146, 37 and 7.0 μg/l, respectively. Uchhali, Khabbaki and Jahlar lake water samples had the mean concentration of: total Se 2103, 670 and 297 μg/l; Se^+VI 1777, 470, and 233 μg/l; Se^+IV 291, 166 and 39 μg/l; Se^-II 35, 34 and 25 μg/l, respectively. The Sakesar limestone Formation of Eocene age rich in shales and fossils (median Se concentration 7.2 μg/kg) are considered to be the source of selenium that have enriched soils of Soan-Sakesar valley. Selenim speciation results show the abundance of selenate in all the environmental samples. A linear relationship between Se^+VI and pH (R²= 0.84, 0.58, 0.88, 0.82, and 0.91; significant at the 0.05 level) for groundwater, saturation extract, stream, spring, and lake waters were noted, suggesting that the Se^+VI in the samples is highly associated with pH. Linear relationships were established between Se^+VI and Mg, NO₃, and SO₄ for groundwater (R²= 0.24, 0.16, and 0.64; significant at the 0.01 level) and surface water (R²= 0.96, 0.14, and 0.91; significant at the 0.001 level). This suggests the high concentrations of Mg, NO₃ and SO₄, which strongly adsorb and compete with selenium for surface site, increases the Se^+VI fraction. The results show that the higher percentage of selenate on other species in the analyzed samples is favored by higher pH and oxidizing environments of the valley.