Unveiling the presence of mixed oxidation states of Europium in Li7+δEuxLa3−δZr2−δO12−δ garnet and its impact on the Li-ion conductivity

Recently, lanthanides have been employed by researchers to examine their impact on the structure and properties of Li₇La₃Zr₂O₁₂ (LLZO) garnets. In this regard, we developed Europium oxide (Eu₂O₃) doped LLZO (Li_7+δEu_xLa_3−δZr_2−δO_12−δ) solid electrolyte which demonstrates a cubic phase with the symmetry of Iad (No.230) at room temperature. In this investigation, different concentrations of Eu ranging from 0.1 to 0.6 atoms per formula unit (pfu) were doped into Li₇La₃Zr₂O₁₂ to evaluate the impact of Eu on the stability of the cubic phase and thereby the ionic conductivity. The results unveiled that upon doping Eu³⁺ ions, the Eu²⁺ state is also formed and is then self-doped into the structure in which Rietveld refinement coupled with XPS, EPR, and solid-state NMR suggests that Eu³⁺ ions most probably partially occupy Zr⁴⁺ (16a) site, the Eu²⁺ ions occupy La³⁺ (24d) site, and the Li⁺ ions occupy two different sites (24d and 96h). It was further found that such a site preference induces distortion at LaO₈ polyhedrons opening up the neck for Li-ions diffusion, thereby enhancing the ionic conductivity. Moreover, it was revealed that Li-ions probably hop from 96h to 24d and then to 96h site to generate the Li-ion movement. Overall, by introducing Eu ions into the LLZO structure, an enhanced bulk ionic conductivity of 0.30 × 10⁻³ S/cm at 298 K with a minimum electronic conductivity of 2.547 × 10⁻⁹ S/cm at 298 K was achieved.     

离子液体在有机合成中的应用

概述了离子液体作为催化剂和绿色溶剂在催化加氢、Diels Alder反应等有机合成反应中的应用,提出离子液体解决了催化剂的回收问题,避免了挥发性溶剂对环境的污染,实现了有机合成的绿色化,展望了离子液体在有机合成中的应用前景。     

Solid polymer electrolytes. XI. Preparation,characterization and ionic conductivity of new plasticized polymer electrolytes based on chemical‐covalent polyether–siloxane hybrids

A new hybrid polymer electrolyte system based on chemical‐covalent polyether and siloxane phases is designed and prepared via the sol–gel approach and epoxide crosslinking. FT‐IR, ¹³C solid‐state NMR, and thermal analysis (differential scanning calorimetry (DSC) and TGA) are used to characterize the structure of these hybrids. These hybrid films are immersed into the liquid electrolyte (1M LiClO₄/propylene carbonate) to form plasticized polymer electrolytes. The effects of hybrid composition, liquid electrolyte content, and temperature on the ionic conductivity of hybrid electrolytes are investigated and discussed. DSC traces demonstrate the presence of two second‐order transitions for all the samples and show a significant change in the thermal events with the amount of absorbed LiClO₄/PC content. TGA results indicate these hybrid networks with excellent thermal stability. The EDS‐0.5 sample with a 75 wt % liquid electrolyte exhibits the ionic conductivity of 5.3 × 10^?3 S cm^?1 at 95°C and 1.4 × 10^?3 S cm^?1 at 15°C, in which the film shows homogenous and good mechanical strength as well as good chemical stability. In the plot of ionic conductivity and composition for these hybrids containing 45 wt % liquid electrolyte, the conductivity shows a maximum value corresponding to the sample with the weight ratio of GPTMS/PEGDE of 0.1. These obtained results are correlated and used to interpret the ion conduction behavior within the hybrid networks. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1000–1007, 2006     

[bupy]BF4-AlCl3离子液体上甲苯和间戊二烯的烷基化反应

The alkylation of toluene with 1,3-pentadiene to produce pentyltoluene was carded out to obtain 2,6-dimethylnaphalene, which is an important intermediate during the production of 2,6-naphthalene dicarboxylic acid. Based on our previous work using anhydrous AlCl3 as catalyst, [bupy]BF4-AlCl3 ionic liquids were employed to catalyze the reaction of 1,3-pentadiene with toluene. The experimental results show that [bupy]BF4-AlCl3 ionic liquids are suitable for the reaction especially when the molar ratio of AlCl3 to [bupy]BF4 is 1.75 ： 1, and the reaction could proceed at the temperature as low as 0℃. It could be as active as pure AlCl3, but much more environmentally friendly.     

离子液体中片状纳米ZnO的制备、表征及其光催化性能

采用一步合成法制备了离子液体1-庚基-3-甲基咪唑溴盐([C7mim]Br),以该离子液体为反应介质,在常压下制备了片状纳米ZnO粉体。用场发射扫描电子显微镜、X射线衍射、傅立叶转换红外光谱等对片状纳米ZnO粉体进行表征,结果表明,在该体系下离子液体作为溶剂及模板剂制备出具有六方纤锌矿结构片状聚集体,平均厚度约为20 nm,平均长和宽约为190 nm。以高压汞灯为光源,以ZnO纳米片为光催化剂,对有机染料罗丹明B进行光降解实验,结果表明,经过145 min后罗丹明B的去除率达到了96.4%,具有良好的光催化活性。     

Viscosity of binary mixtures. I. mono-, di-, and tri-n-butyl and -n-octylamine with cyclohexane

Viscosities for six binary mixtures of n-butylamine, di-n-butylamine, tri-n-butylamine, n-octylamine, di-n-octylamine, and tri-n-octylamine with cyclohexane have been measured at 303.15 K with an Ubbelohde suspendedlevel viscometer. Deviations of viscosities from a rectilinear dependence on mole fraction are attributed to H-bonding and to the size of alkylamine compounds. The application of the Eyring's theory of activation energy is examined. The free volume theory of Prigogine-Flory-Patterson (PFP) and the experimental excess enthalpy have been used to estimate excess viscosity ln = (ln / ₁ ⁰ – x ₂ ln ₂ ⁰ / ₁ ⁰ ) and corresponding free volume, enthalpy, and entropy contributions for five binary mixtures of tri-n-alkylamine: triethyl, tripropyl, tributyl, trihexyl, and trioctylamine with cyclohexane. A comparison of experimental and theoretical excess viscosities indicates a failure of the PFP theory when two components of the mixture differ considerably in size. The size difference contribution to excess viscosity is related to (V ₂ ^*1/2 – V ₁ ^*1/2 ), where V ₁ ^* and V ₂ ^* are hard-core volumes of two components of the mixture.     

离子液体辅助提取葡萄籽中原花青素的工艺研究

原花青素是最有效的天然抗氧化剂,具有清除自由基,防癌抗衰老,美容养颜的功效.以赤霞珠葡萄籽为原料,通过添加优选离子液体1-丁基-3-甲基咪唑氯盐([Bmim]Cl)的乙醇水溶液提取原花青素,考察了提取温度、提取时间、乙醇体积分数、液料比4个因素对原花青素提取效率的影响.根据单因素实验结果设计响应面实验,得到原花青素的最佳工艺参数.该工艺的开发为原花青素的工业生产提供参考.     

多元醇胺对钢铁渣粉溶解特性的影响

为了解决钢铁渣粉溶解性差所引起的活性低的问题,研究了三乙醇胺( TEA)、三异丙醇胺( TIPA)和二乙醇单异丙醇胺( DEIPA)对钢铁渣粉在碱性环境下溶解的影响规律,通过电导率仪、酸度计、电感耦合等离子体原子发射光谱仪( inductively coupled plasma atomic emission spectroscopy,ICP-AES)和八通道微量热仪对钢铁渣粉的溶解特性进行了表征。结果表明：多元醇胺降低了钢铁渣粉液相的pH并提高了液相电导率,主要表现为增加了液相中Fe、Ca、Al元素的质量浓度,其中TEA和DEIPA的影响效果大于TIPA;多元醇胺提高了钢铁渣粉早期的溶解热和最大水化热峰值,进一步证实了多元醇胺对钢铁渣粉具有增溶作用。     

UNIFAC模型关联CH_3OH/C_2H_5OH-[Mmim]DMP体系的汽液相平衡

基于基团贡献法,采用UNIFAC模型关联了已有实验数据的吸收式制冷循环工质对甲醇-1,3-二甲基咪唑磷酸二甲酯盐(CH3OH-[Mmim]DMP)和乙醇-1,3-二甲基咪唑磷酸二甲酯盐(C2H5OH-[Mmim]DMP)体系的汽液相平衡数据.获得了新基团[mim]DMP和其他基团间的UNIFAC相互作用参数,扩充了UNIFAC模型的应用范围.用拟合的基团相互作用参数计算了CH3OH-[Mmim]DMP和C2H5OH-[Mmim]DMP体系的的汽液相平衡数据,并同实验数据进行了比较,平均相对偏差(ARD)分别为0.91%和2.39%.说明采用UNIFAC模型预测效果很好,能够很好描述二元体系的VLE行为.最后,对CH3OH-[Mmim]DMP和C2H5OH-[Mmim]DMP体系的蒸气压数据进行了比较,发现离子液体[Mmim]DMP的与乙醇的亲和性要强于甲醇,C2H5OH-[Mmim]DMP体系更具有成为吸收式制冷循环工质对的潜力.     

氯化锂对纤维素/离子液体浓溶液纺丝的影响

以离子液体1-烯丙基-3-甲基咪唑氯盐（[AMIM]Cl）为溶剂、氯化锂（LiCl）为添加剂,通过测定纤维素溶液的流变性能来考察LiCl对纤维素/[AMIM]Cl溶液纺丝性能的影响,发现纤维素/[AMIM]Cl/LiCl呈现切力变稀行为,当LiCl添加量为[AMIM]Cl质量的3%时,切力变稀行为最明显.使用双螺杆挤出机通过干湿法纺丝制备出了高浓度的纤维素纤维,通过XRD、偏光显微镜、SEM及单纤强力仪等表征了纤维的结构与性能,结果表明随着LiCl含量的增加,所得纤维的结晶度和双折射率增加,结构致密,纤维强度增加,当LiCl含量达3%时,纤维强度可达3.13 cN/dtex.