离子液体[BMIM][BF_4]水溶液比热容及热工特性分析

离子液体在化工和能源领域应用研究中,其比热及热工特性尤为重要,然而目前相关的比热数据较缺乏.研究主要对离子液体[BMIM][BF4]及其水溶液的比热容进行了测定.测试系统采用耐驰DSC204HP低温高压差热仪,测试精度较高且稳定可靠.实验测试的温度范围为273.15K~423.15K,测试的离子液体摩尔浓度分别为1.0...     

离子液体[BMIM]BF4+H2O汽液相平衡实验研究

离子液体[BMIM]]BF4具有较高的热稳定性,且与水有很好的互溶性,其水溶液在分离、萃取等化工和制冷、热泵等吸收式能量转换系统中的应用受到重视,急需较完整的相平衡实验数据.本文对离子液体[BMIM]BF4+H2O二元体系的汽液相平衡(蒸汽压)特性进行较大温度和压力范围的测定.测试系统采用了双温浴控温方式,获得较高测试...     

聚噻吩在离子液体中的电化学合成研究

在 1 丁基 3 甲基咪唑六氟磷酸盐离子液体 (BMIM)PF6 中直接电化学合成制备了聚噻吩膜 .通过红外光谱 (FT IR)和扫描电子显微镜 (SEM)对聚噻吩膜的结构和形貌进行了表征 .利用紫外可见光谱 (UV Vis)、循环伏安法 (CV)和四探针法研究了聚噻吩膜的电子和电化学特性 .研究结果表明 ,在电位 1.7～ 1.9V(相对于Ag/AgCl) ,在(BMIM)PF6 中可以制备均匀的聚噻吩膜 ,其中 ,离子液体 (BMIM)PF6 既作为溶剂又作支持电解质 ;在离子液体中制备的聚噻吩膜具有良好的稳定性和充放电能力 ,聚噻吩膜的电导率在 0 .0 1～ 0 .1S/cm .     

(火积)耗散原理在相变储热过程优化中的应用

为了强化相变储热单元的储热性能,基于(火积)耗散原理,数值分析了相变材料的熔点对储热单元的储热速率、(火积)耗散率及储热品质的影响。结果表明:对于单级相变储热单元,相变材料熔点越低,相变储热过程的传热速率就越高,而对应的(火积)耗散率就越大,储存热量的品质也越低。证明了(火积)耗散原理用于相变储热过程优化的可行性。对于两级相变储热单元的分析结果表明,合理的匹配两级相变材料的熔点,可以实现储热速率高于单一相变材料,且传热过程的不可逆性((火积)耗散率)低于单一相变材料。可见,多级相变材料的合理匹配,可以同时提高储热速率、降低储热过程的不可逆性。     

离子液体凝胶聚合物电解质PP13TFSI-LiTFSI-P(VdF-HFP)的电化学性能 (cited: 1)

采用溶液浇铸法将N-甲基-N-丙基哌啶二(三氟甲基磺)亚胺(PP13TFSI)、二(三氟甲基磺)亚胺锂与偏氟乙烯-六氟丙烯共聚物(P(VdF-HFP))混合制备离子液体凝胶聚合物电解质(ILGPEs). 通过扫描电子显微镜观察发现,这种离子液体凝胶聚合物电解质由于液体相的均匀分布而具有疏松的结构. 采用电化学阻抗、计时电流法、线性扫描伏安法测试了电解质的离子电导率、锂离子迁移数和电化学窗口. 室温下离子液体凝胶聚合物电解质的离子电导率和锂离子迁移数分别是0.79 mS/cm和0.71,电化学窗口为0～5.1 Vvs. Li⁺/Li. 电池性能测试表明,这种离子液体凝胶聚合物电解质在Li/LiFePO₄电池中是稳定的,放电容量在30、75和150mA/g倍率下分别为135、117和100 mAh/g,电池经100个循环后容量保持在100%而几乎没有衰减.     

Co(S1-xSex)2系统中的铁磁量子相变

针对Co(S1-xSex)2系统在x=0.11附近发生的铁磁金属到顺磁金属相变,制备了一系列不同Se替代浓度的多晶样品.通过对其结构和电阻率-温度ρ(T)关系的系统观测,结果发现,样品铁磁相变温度TC随着Se替代浓度x值的增加,以(1-x)1/2关系单调下降,其二级铁磁相变转变为一级相变;在临界浓度x=0.11附近,其ρ(T)关系由Fermi液体行为转变为非Fermi液体行为.作者认为,Co(S1-xSex)2系统在x=0.11附近发生的是一种量子相变,在该量子相变点附近零温度下的自旋量子涨落导致其ρ(T)关系的反常行为.     

三角晶场中4A2(3d3)态离子全组态EPR理论研究

在中间场耦合图像中,建立了＾４Ａ２（３ｄ＾３）态离子全组态ＥＰＲ理论;研究了ＥＰＲ参量随三角晶参量Ｖ、Ｖ＇及立方晶场参量Ｄｑ变化关系;用完全对角化方法验证了Ｍａｃｆａ５ｌａｎｅ ＥＰＲ的三阶微扰公式,结果表明,在较大的晶场范围内微扰公式的收敛性很好;研究了ＥＰＲ参量的微观起源及自放二重态对ＥＰＲ参量的贡献,指出自旋二重 对零场分裂参量的贡献不可忽略,二重态对ｇ因子的贡献甚微。     

金(I)催化丙二烯基化合物构建螺环[4,5]癸烷骨架的计算研究

采用B3LYP-D3(BJ)计算方法研究了金催化丙二烯基化合物合成螺环[4,5]癸烷骨架的反应机理。通过SMD模型在实验对应的CH3CN溶剂体系中进行单点能量计算得出更准确的能量。计算研究表明,该反应包括三个主要的步骤：烯丙基和乙烯基端基碳原子的分子内环加成、四元环重构为五元环的半频哪醇重排过程、消除反应释放催化剂并得到产物。结果显示第一步是反应的决速步骤,其活化自由能相对较低为70.18 kJ/mol,表明金催化的合成反应在室温条件下能够发生。     

TCs-Fe(Ⅲ)体系离子液体气浮浮选荧光光谱法分离/富集四环素类抗生素残留的研究

将离子液体应用于气浮溶剂浮选,建立了一种分离/富集四环素类(tetracyclines, TCs)抗生素的新方法——离子液体气浮溶剂浮选。最优化浮选条件为：以1-己基-3-甲基咪唑六氟磷酸盐([Hmim]PF₆)和乙酸乙酯(EA)的混合溶剂(φ=1/0.9)为浮选剂,以Fe(Ⅲ)为捕集剂,pH值为7.6,气体流速为40 mL·min-1,浮选时间为50 min。富集TCs-Fe(Ⅲ)配合物的[Hmim]PF₆-EA相用荧光光谱法直接测定,其线性回归方程为F=246.5c+4.32(c: μg·10 mL-1),相关系数r=0.999 1。实测了鱼塘表面水体和沉积物中四环素类抗生素的含量,加标回收率达到94.2%～100.4%,RSD＜3.2%(n=5)。红外光谱分析显示TCs-Fe(Ⅲ)配合物没有和离子液体发生反应,离子液体在气浮溶剂浮选中只起到溶剂作用。该方法适合于环境水样中痕量四环素类抗生素的分离/富集及分析。     

Tm3+离子掺杂的钨酸钇钠晶体中浓度猝灭效应的研究

测量了Tm3+离子不同浓度(0.5at.%,3 at.%,5 at.%)掺杂的NaY(WO4)2晶体在800 nm激光二极管激发下的上转换发射光谱.结合吸收谱、荧光谱和由Judd-Ofelt理论计算的光谱参数,详细分析了Tm36:NaY(WO4),晶体中上转换能量传递机理和离子浓度对上转换发射的影响.讨论了四种影响上转换发光效率的离子间相互作用机理:3H5+1G4→3H6+1D2,3H5+3H5→3H6+3F3,1G4+3H6→3F4+3F3,1G4+3H6→3F3+3F4,并根据Miyakawa-Dexter理论定量计算了各过程的发生概率.论证了交叉弛豫和共协上转换等浓度猝灭效应是影响Tm3+离子蓝色上转换荧光发射效率的主要因素.     

Miscibility and Hydrogen Bonding Interactions in Blends of Poly(hydroxyether ketone) and Poly(4-vinyl pyridine)

The influence of silica nanoparticles on the tensile properties of poly(ethylene terephthalate)(PET) fibers was investigated. The results showed that mechanical properties of PET fibers were improved through nano‐silica incorporation. Two maxima of the modulus‐strain curves of PET/silica nanocomposites (PETS) fibers are always higher than those of pure PET (PET0) fibers. The results of microstructure investigations suggested that the amorphous orientation factor of PETS fibers is higher than that of PET0 fibers. It is suggested that the increase of amorphous orientation factor contributed to the improvement of tensile properties of PET fibers. Considering the difference in modulus‐strain curves of PET0 and PETS fibers, it is believed that the addition of nanoparticles not only improved the amorphous orientation factor but also changed the load units of PET fibers when strained, which also resulted in the improvement of tensile properties.     

Phase Ordering and Crystallization Kinetics in Ultrathin Poly(ethylene oxide)/Poly(methyl methacrylate) Blend Films

Crystallization in ultrathin Poly(Ethylene Oxide)/Poly(Methyl Methacrylate) (PEO/PMMA) blend films with thickness of ca. 10 nm was investigated by means of microscopic and in situ spectroscopic methods. It was revealed that the blend films undergo a phase ordering in a humid atmosphere before or during crystallization, with PEO de-mixing with PMMA and segregating to the free film interface on the PMMA layer. The de-mixed PEO chains crystallize into a fractal-like morphology by a diffusion-limited process, and the crystal growth is 1-dimensional with Avrami exponent n ≈ 1, resulting in flat-on crystal lamellae with the PEO chains oriented normal to the film plane.     

Core–Shell Poly (Ionic Liquid)@Mesoporous Silica Chemiluminescent Nanoprobes for Sensitive Intracellular Hydrogen Peroxide Imaging

Despite significant developments in spatial distribution imaging of H₂O₂ as one the most important nonradical reactive oxygen species, novel background‐free, highly sensitive, and selective probes that allow intracellular sensing are still imperative. This is mainly because the fluorescent probes usually suffer some drawbacks such as, fluorescence bleaching and requirement of bulky light sources. In this study, the rational design and fabrication of a nonenzymatic nanoprobe (c‐PIL@mSiO₂) with dramatically improved sensitivity for chemiluminescent (CL) imaging of intracellular and in vivo H₂O₂ at nano molar level is presented. The limit of detection is lower than the endogenous H₂O₂ concentration, and is significantly better than that of some recently reported fluorescent and CL probes. Structurally, the nanoprobe is composed of a unique amphiphilic poly(ionic liquid) core for preserving H₂O₂ responsive reagents, and a mesoporous silica shell acts as an “exoskeleton” to provide hydrophilic nature. The multiple alternating hydrophobic and hydrophilic nanodomains of the poly(ionic liquid) core increase mass transfer dynamics, which increase the sensitivity of H₂O₂ imaging. RAW264.7 macrophages and mice models of inflammations experiment show that the c‐PIL@mSiO₂ is capable of imaging H₂O₂ intracellular and in vivo. This probe for the first time achieves CL detection of endogenous intracellular H₂O₂ without disruption of cells.     

Intermolecular Hydrogen Bonding of Poly(Imino Imino Ketone Ketone)

Molecular dynamics calculations were made of the distance from the hydrogen atom of the imino group to the distance of the oxygen atom of the carbonyl group of poly(imino imino ketone ketone) (PIIKK). The results showed that theoretically there was hydrogen bond formation between the hydroxyl group and the carbonyl group of PIIKK. The existence of the hydrogen bonding between the polymer chains of PIIKK was confirmed by infrared spectrum analysis. Due to the existence of the hydrogen bonding, the glass transition temperature increased to 273°C from 143°C for poly(ether ether ketone) (PEEK).     

Electrodeposition of Poly(3-Chlorothiophene) Film on WO3 Surfaces in an Ionic Liquid

Poly(3-chlorothiophene) (PCT) was electrochemically polymerized on the surface of tungsten oxide (WO₃) in the ionic liquid 1-butyl-3-metyllimidazolium hexafluorophosphate by a potentiodynamic method. The PCT/WO₃ films were characterized by Fourier-transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analysis. Cyclic voltammetric experiment results showed that the electrochemical activity of the PCT/WO₃ composite film was significantly improved due to the contribution of unique structure and interactions between PCT and WO₃.     

Electrochemical switching of fluorescence from europium ions dissolved in poly(ethylene oxide) oligomers

Europium salts were dissolved in poly(ethylene oxide) (PEO) oligomers. The europium ions were revealed to be electrochemically redox-active in PEO oligomers. Trivalent europium ions (Eu³⁺) showed red fluorescence (λ_em = 614 nm) in PEO oligomers, and a new intensive blue fluorescence (λ_em = 450 nm) was obtained after reducing the Eu³⁺ into Eu²⁺ by giving negative potential (−0.7 V versus Ag). Reversible fluorescence switching was also carried out by changing the given potential alternately. Sufficient color change required about 20 min because of slow electrode reaction. The fluorescence intensity from europium ions was affected by the molecular weight of matrix PEO. The amount of terminal hydroxyl groups and local viscosity were revealed to affect the fluorescence as the vibrational quenching and diffusion coefficient, respectively. The PEO oligomer with average molecular weight of 600 gave the most intensive fluorescence.     

Ionic conductivity of electrolytes based on star-branched poly(ethylene oxide) with high concentration of lithium salts

Electrolytes based on star-branched poly(ethylene oxide) with lithium bis(trifluoromethanesulfone)imide LiTFSI and lithium iodide salts were prepared by casting from solution. The electrical properties of electrolytes subjected to various heating and cooling runs were studied by impedance spectroscopy and impedance spectroscopy simultaneous with optical microscope observation. Differential scanning calorimetry was used for additional characterization. The results indicate that in electrolytes with high content of salt, values of ionic conductivity comparable to that of dilute electrolytes can be achieved. Moreover, electrolytes with high amount of salt seem to show weaker temperature dependence of conductivity. Promising results in terms of ionic conductivity were obtained for mixture of LiTFSI and lithium iodide. A few problems which may decrease the performance of studied system as a solid electrolyte were also identified, from which changes of physical properties of samples subjected to thermal cycles and aging seem to be the most important ones.     

High-Pressure Analysis of the Multiple Melting Endotherms of Poly(ethylene succinate) and Poly(butylene succinate)

The origin of the multiple melting peaks in two linear polyesters, poly(ethylene succinate) (PES) and poly(butylene succinate) (PBS), of isothermally crystallized samples was investigated by differential scanning calorimetry (DSC) at atmospheric pressure and high-pressure differential thermal analysis (HP-DTA) at elevated pressures. In PES, the DSC melting curves showed three endothermic peaks at slow heating rates, which decreased to two with increasing heating rates. The HP-DTA curves showed that the area (qualitative) and peak height of the high-temperature peak decreased with increasing pressure and merged with the low-temperature peak at pressures above 450 MPa. This behavior supported the melting, recrystallization, and remelting model for the observed multiple melting endotherms. In PBS, the DSC melting curves were similar to those seen in PES. The HP-DTA curves were also similar to PES up to 400 MPa, but above this pressure the area and the peak height of the high-temperature peak and the temperature difference between the high- and low-temperature peaks remained unchanged. This observation suggested that the two peaks in PBS were due to the melting of two populations of crystals with different lamellar thickness originally present in the sample. The multiple melting behavior in isothermally crystallized PBS is proposed to incorporate both the melting of two populations of crystals and melting, recrystallization, and remelting.     

Preparation and Characterization of Poly(ethylene oxide)/Graphene Nanocomposites from an Aqueous Medium

The nanocomposite films of a functionalized graphene sheet (FGS) and poly(ethylene oxide) (PEO) were cast from the physical blend of an aqueous FGS dispersion assisted by sodium dodecyl sulfate and an aqueous PEO solution. The thermal properties observed by differential scanning calorimetry suggested that FGS had a nucleating effect on the PEO crystallization. However, we found FGS actually hindered the growth of PEO crystals. The dynamic mechanical properties indicated that FGS effectively reinforced the matrix PEO. The FGS also efficiently improved the electric conductivity of PEO. With the addition of 2 parts of FGS per 100 parts of PEO, the conductivity was increased by more than 10³-fold from that of pristine PEO.