银掺杂改性蒙脱土修饰电极上对苯二酚的电化学行为与测定

利用十八烷基三甲基溴化铵(STAB)和银氨溶液制备了银掺杂改性蒙脱土,并用X射线衍射法、扫描电镜法和交流阻抗法对其进行表征.用循环伏安法(CV)研究了对苯二酚在银掺杂改性蒙脱土修饰电极上的电化学行为,测定了部分动力学参数.结果表明,对苯二酚在电极上的阳极过程受吸附-扩散混合控制,阴极过程受扩散控制,转移的电子数n和质子...     

以C_(70)衍生物为电子受体的高效聚合物固体薄膜太阳能电池

以PC[70]BM(phenyl C71-butyric acid methyl ester)取代PC[60]BM(phenyl C61-butyric acid methyl ester)作为电子受体材料,以MEH-PPV(poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene])为电子给体材料,制成了本体异质结(bulk heterojunction,BHJ)聚合物太阳能电池.MEH-PPV/PC[70]BM器件在AM1.5G(80 mW/cm2)模拟太阳光的光照条件下得到了3.42%的能量转换效率,短路电流值达到了6.07 mA/cm2,开路电压0.85 V,填充因子为53%.通过紫外可见吸收光谱和外量子效率的研究,发现PC[70]BM作为电子受体,对扩大光谱的吸收范围和增加活性层的吸收系数有明显的作用.同时比较了不同溶剂对该体系器件性能的影响.通过原子力显微镜(AFM)、光暗导I-V曲线等研究,分析了1,2-二氯苯有利于给体相和受体相的微相分离和载流子的传输的原因.     

Electrochemical and optical characterization of p- and n-doped poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene

We study electrochemical p- and n-type doping in the well-known light-emitting polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV). Doping reactions are characterized using cyclic voltammetry. Optical measurements including photoluminescence and UV/Vis/NIR transmission were performed on doped samples. We find that oxidation in MEH-PPV is a highly reversible reaction resulting in stable freestanding doped films, while the reduced form is unstable and the reaction irreversible. We discuss the dependence of doping reactions on scan rate, film thickness, salt type and concentration, and working electrode type. We observe the development of two additional broad absorption bands in both lightly and heavily doped films accompanied by a slight blueshift in the primary optical transition, suggesting bipolaron band formation. Finally we find that both p and n dopings result in extremely sensitive photoluminescence quenching. We propose a physical model for understanding electrochemical doping in MEH-PPV and the implications this has on the development of such technologies as polymer light-emitting electrochemical cells, electrochromic devices, actuators, and sensors.     

离子液体电解质种类对活性炭电极超级电容器电化学性能的影响

本文将经水蒸气二次活化的椰壳活性炭（W-AC）作为电极材料,选择1-乙基-3甲基咪唑四氟硼酸盐（[EMIM]BF₄）作为电解质,结果表明W-AC电极的比电容量远高于未活化的椰壳活性炭（R-AC）.使用循环伏安、恒电流充放电、交流阻抗等方法研究了不同种类离子液体电解质对超级电容器电化学性能的影响.不同阴阳离子组成的离子液体作为电解质,直接影响超级电容器的电化学性能. 研究表明,由EMIM⁺和BMIM⁺阳离子与BF₄^-、TFSI^-阴离子构成的离子液体电解质较适用于W-AC电极. 其中在[EMIM]BF₄电解质中,单片电极的比电容量可高达153 F·g^-1;在1-丁基-3-甲基-咪唑四氟硼酸盐（[BMIM]BF₄）电解质中电位窗可达3.5V,能量密度可高达57 Wh·kg^-1.本研究对于构筑高性能超级电容器离子液体的选择提供参考,以满足不同应用领域需求.     

噻虫胺分子印迹电化学传感器的制备与应用EI北大核心CSCD

以噻虫胺为模板分子,通过恒电位沉积壳聚糖,在还原氧化石墨烯(RGO)修饰的玻碳电极表面制备了可特异性识别噻虫胺的分子印迹传感器。采用交流阻抗法(EIS)、差分脉冲伏安法(DPV)和循环伏安法(CV)对传感器的电化学性能进行表征,优化了电沉积时间、洗脱圈数、孵化时间及溶液pH等实验条件。在优化条件下,以K_(3)[Fe(CN)_(6)]作为电活性探针,DPV峰电流强度与噻虫胺浓度在1.0~1000 nmol/L范围内呈良好的线性关系,检出限0.46 nmol/L。将本方法应用于实际样品中噻虫胺的含量测定,加标回收率为97.6%~103.2%。     

Fluorescence Quenching of Poly[2-methoxy-5-(2''''-ethylhexoxy)-p-phenylene vinylene](MEH-PPV) in Solutions

Introduction Poly(1,4-phenylene vinylene) (PPV) has been the subject of explosive interest in these years. It has poten-tial applications in light-emitting diode, light emitting electrochemical cell and plastic laser.1-4 To improve its solubility and optical properties substituents are intro-duced to the PPV main chain. Poly[2-methoxy-5-(2'-ethylhexoxy)-p-phenylene vinylene] (MEH-PPV) is one of derivatives with alkoxy groups on phenyl rings. It exhibits superior solubility in organic sol…     

Application of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] for splitting of single-walled carbon nanotube bundles in polystyrene/SWCNT composite

Dispersions of single-walled carbon nanotubes (SWCNTs) in organic solutions containing poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) were studied by Raman spectroscopy, UV-vis-NIR spectroscopy, and electron microscopy. This polymer interacts with the nanotube resulting in the appearance of a new red-shifted absorption band in the electronic spectrum. This indicates the formation of a charge-transfer complex between MEH-PPV and SWCNTs. Additives of MEH-PPV make it possible to achieve stable suspensions of nanotubes in styrene. A polystyrene/SWCNT/MEH-PPV composite with a high degree of bundle splitting was obtained by polymerization. It was shown that the luminescence intensity of the nanotubes in the Raman spectrum can serve as a indicator for the estimation of the degree of splitting of SWCNT bundles in the composite.     

联萘酚与固体支撑双层类脂膜相互作用

采用循环伏安法、交流阻抗法研究了联萘酚(BINOL)与固体支撑双层类脂膜(s-BLM)之间的相互作用.结果表明,联萘酚通过氢键、疏水作用与s-BLM发生相互作用.随着相互作用时间的延长,联萘酚/s-BLM体系中的氧化峰电流先增大后减小,表明联萘酚逐渐破坏s-BLM的整体性,诱导膜内部形成微孔通道.联萘酚的浓度越大,联萘酚分子通过s-BLM的渗透时间越短.此外,随着卵磷脂浓度和胆固醇含量的增加,s-BLM的膜电阻变大,联萘酚渗透通过s-BLM速率减小,导致其对s-BLM的渗透性能减弱.     

Raman spectroscopy of intermolecular charge transfer complex between a conjugated polymer and an organic acceptor molecule

Intermolecular donor-acceptor charge transfer complex (CTC) formed in the electronic ground state between poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and 2,4,7-trinitrofluorenone (TNF) has been investigated by Raman and optical absorption spectroscopies. Blending of MEH-PPV and TNF results in appearance of the CTC absorption band in the optical gap of the both components and in changes in the characteristic MEH-PPV Raman bands including shifts, change in bandwidth, and intensity. The experimental data are similar in films and solutions indicating the CTC formation in both. We associate the low-frequency shift of the strongest MEH-PPV Raman band at approximately 1580 cm(-1) reaching 5 cm(-1) with partial electron transfer from MEH-PPV to TNF amounting approximately 0.2e(-). We suggest that polymer conjugated segments can form the CTC of variable composition MEH-PPV:TNF=1:X, where X相似文献   

Labeless Immunosensor Assay for the Stroke Marker Protein S-100[β] Based Upon an AC Impedance Protocol

We developed label less immunosensors for the stroke marker protein S-100[β], utilizing polyaniline electrode microarrays as substrates to immobilize biotinylated S-100[β] antibodies using classical affinity approaches. The AC impedance studies, before and after exposure to solutions of S-100[β], showed increasing antigen concentration caused increases in the real component of the impedance. Subtracting specific and non-specific antibody responses eliminated non-specific adsorption effects. Linear impedimetric responses toward S-100[β] in buffer solutions over a concentration range of 0–50 pg ml^?1 were observed. The limit of detection of the immunosensor was 1 pg ml^?1 S-100[β], discrimination was possible at 10 pg ml^?1.     

Effects of annealing treatment on the properties of MEH-PPV/titania hybrids prepared via in situ sol-gel reaction

A uniform poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV)/titania hybrid film was successfully prepared by an in situ sol-gel reaction of titanium isopropoxide (TIP) in the presence of MEH-PPV/2-chlorophenol solution. The annealing treatment increased the conversion of TIP to titania as determined from evidence of the formation of Ti-O-Ti bonds in the Fourier transform infrared (FTIR) spectrum. Scanning electronic microscope (SEM) photographs showed that the morphology and distribution of titania in the hybrid film were strongly related to the amount of water in the in situ sol-gel reaction. The thermal stability of MEH-PPV/titania hybrids was enhanced by the annealing treatment. Small angle X-ray scattering (SAXS) and X-ray diffraction (XRD) analyses indicated that annealing treatment promoted the ordered aggregation of the MEH-PPV chains and crystallization of titania to a certain extent. The blue shift in Ultraviolet-visible (UV-vis) absorption of pure MEH-PPV after annealing was ascribed to the small extent of decomposition and coil conformation which occurred at high temperature. A more-obvious blue shift for the hybrids was observed, which resulted from irregular aggregation and coil conformation of the MEH-PPV chains induced by heterogeneous point, TIP (titania). The red shift in the photoluminescent (PL) emission for pure MEH-PPV resulted from a certain extent of ordered aggregation after annealing. However, only a slight red shift in the PL emission peak for the hybrids was found due to the hindrance of ordered aggregation of MEH-PPV chains in the presence of TIP (titania).     

Effect of metal nanoparticles on the optical properties of the solutions of porphyrinates and MEH-PPV polymer

The interactions of metal nanoparticles, which were synthesized in inverse micelles, with a number of porphyrinate molecules and a poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) polymer in solutions were examined by spectrophotometry in order to study the effects of various additives on the efficiency of sun energy absorption and conversion by photosensitive polymer layers. The optical absorption and luminescence spectra of the solutions of Ag, Pd, and Pt nanoparticles and the solutions of Pd(II) and Pt(II) meso-tetra(benzo-15-crown-5)porphyrinates and the MEH-PPV polymer were measured previously.     

Studies on interaction of porphyrin and its complexes with DNA at interface on gold electrode modified by thiol-porphyrin self-assembled monolayer

The interaction of 5-[p-(mercaptopropyloxy)-phenyl]-10, 15, 20-triphenylporphyrin (H₂MPTPP) and its metalloporphyrin (Co, Ni-MPTPP) with calf thymus deoxyribonucleic acid (DNA) has been studied on gold electrode modified by thiol-porphyrin self-assembled monolayer (SAM). The mode and characteristics of their interaction with DNA have been studied by cyclic voltammetry, scanning electrochemical microscope (SECM), and alternating current (AC) impedance. Some electrochemical parameters have been determined, i.e., apparent heterogeneous reaction rate constant (k _eff from SECM and k _f from AC impedance) and the hindrance (B) of electrode. K₃[Fe(CN)₆] was used as probe to obtain some electrochemical information of electrode interface. SECM images obtained from interface on SAM interacted with DNA showed very good resolution with different topography. Based on a comparison with the results from experiments, a reasonable agreement between SECM and AC impedance can be obtained, which means a conjunction of them. It is proposed to be electrostatic interaction of H₂MPTPP, Co-MPTPP and Ni-MPTPP with DNA, and the attractive force between porphyrins and DNA follows the order Ni-MPTPP > Co-MPTPP > H₂MPTPP.     

聚邻苯二胺/镍氢氧化物修饰电极的研究

采用循环伏安法(CV)在聚邻苯二胺修饰玻碳电极表面络合Ni2+,然后将其置于NaOH溶液中CV扫描成功制备了镍氢氧化物/聚邻苯二胺/玻碳修饰电极(Ni(OH)2/PoPD/GC).通过CV探讨了聚合和负载机理,电化学交流阻抗谱(EIS)表征了电极修饰过程中界面阻抗变化,扫描电镜表征了PoPD膜负载Ni(OH)2后的形态...     

Electronic and conformational properties of the conjugated polymer MEH-PPV at a buried film/solid interface investigated by two-dimensional IR-visible sum frequency generation

We present the first measurement of the buried surface electronic states of the conjugated polymer poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylenevinylene] (MEH-PPV) using two-dimensional (2D) IR-visible sum frequency generation (SFG). SFG electronic spectra were obtained by scanning the frequencies of both incident visible and IR beams and used to study the surface electronic transitions associated with the C-C stretching of benzene rings located at the backbone of MEH-PPV. Because of the surface confinement effects, the polymer conformation, and consequently the electronic states, at the film/solid interface are different from those of the bulk film. Theoretical analysis based on an oligomer model was employed to estimate the conjugation-length distributions of MEH-PPV at interfaces. Assuming a Gaussian conjugation-length distribution, it was found that the conjugation-length distribution at the MEH-PPV/solid interface was centered at 5.8 monomer units. Similar surface effects were also observed at the air/polymer interface, with a shorter average conjugation length of 5.1 monomer units.     

Efficient deep-red organic light-emitting diodes based on blending MEH-PPV with a small molecule compound

Efficient deep-red organic light-emitting diodes(OLEDs) were investigated based on the blend of poly[2- methoxy-5-(2’-ethyl-hexyloxy)-l,4-phenylene vinylene](MEH-PPV) with 4,7-bis(5-(7-(9H-carbazol-9-yl)-9,9-dioctyl-9H-fluoren -2-yl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole(compound 1).By optimizing the blend ratio,the turn-on voltage of the devices was significantly reduced from 4.9 V to 2.4 V.A highest external quantum efficiency of 2.56%was achieved at a blend ratio of 95:5(wt) for compound 1:MEH-PPV.The CIE coordinate was measured to be(0.70,0.30),with the luminescence peak at around 680 nm.Based on experimental observations the improvement mechanism is described.     

MEH-PPV和PCBM共混体系光电池中电荷传输及性能与光强的关系

以MEH-PPV{poly[2-methoxy-5-(2'-ethylhexoxy)]-1,4-phenylene vinylene}作为电子给体材料, PCBM[1-(3-methoxycarbonyl)-propyl-1-1-phenyl-(6,6)C61]作为电子受体材料, 制成了共混体系的高性能太阳电池. 光电池在100 mW/cm2强度光照下, 其开路电压Voc为0.8 V, 短路电流密度Jsc为5.06 mA/cm2, 填充因子FF为48.1%, 能量转换效率η为1.93%. UV-Vis及PL图表明, MEH-PPV与PCBM之间没有发生化学变化, 但有明显的荧光猝灭, 说明光生激子能有效地快速分离, 并在各自的传输网络中传递. 分析了光照及暗导I-V曲线的物理意义, 探讨了MEH-PPV与PCBM之间的电荷传输, 研究了在不同强度的光照下器件性能的变化. 随着光强的增加, 器件的短路电流密度线性增大, 开路电压也略有升高, 并联电阻和填充因子下降, 串联电阻变化不明显. 分析了其物理机理, 并进行了合理的解释.     

Enhanced electrochromic absorption in Ag nanoparticle embedded conjugated polymer composite films

Ag/MEH-PPV {poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]} composite films were prepared by the pulse current electrodeposition of Ag nanoparticles followed by spin coating of MEH-PPV and their enhanced electrochromic coloration was investigated. A relatively uniform Ag nanoparticle array was obtained by the electrodeposition and distinct plasmon absorption bands of Ag nanoparticles were observed. The absorption maximum of Ag/MEH-PPV was much higher than that of MEH-PPV, indicating that the Ag nanoparticles induced an enhanced absorption. In addition, the electrochromic absorption was 1.6 times higher at 500 nm wavelength, with a clearly different coloration compared to MEH-PPV.     

LiNi0.49Mn1.49Y0.02O4的合成及其电化学性能研究

应用柠檬酸辅助溶胶-凝胶法.合成了Y3+掺杂的尖晶石LiNi0.49Mn1.49Y0.02O4材料.XRD、循环伏安、恒流充放电和交流阻抗测试结果表明,Y3+的掺杂能提高LiNi0.5Mn1.5O4的倍率和循环性能.在电压区间3.5～4.9V,1C倍率下,其初始放电比容量为114.9 mAh.g-1,100次循环后放电比容量仍可达113.0 mAh.g-1,容量保持率为98.3%.掺杂Y3+能减小材料界面阻抗.     

Vinyl copolymers containing pendant 1,3,4-oxadiazole chromophores: Preparation and electrochemical and electroluminescent properties

Three vinyl copolymers (P1–P3) containing pendant aromatic 1,3,4-oxadiazole derivatives were prepared from their precursor poly(styrene-ran-4-vinylbenzyl chloride) (weight-average molecular weight = 11,400, polydispersity index = 1.18), which had been synthesized by controlled radical polymerization (reversible addition–fragmentation chain transfer). The copolymers were readily soluble in common organic solvents and were basically amorphous materials with 5% weight loss temperatures higher than 360°C. The photoluminescence spectroscopy results revealed that the architectures of P2 and P3 suppressed aggregate formation in the solid state. The LUMO levels of P2 (−3.10 eV) and P3 (−3.09 eV), estimated from cyclic voltammetry data, were much higher than that of P1 (−3.81 eV). The HOMO levels were in the order of P3 (−5.37 eV) > P2 (−5.77 eV) > P1 (−5.96 eV). However, both the HOMO and LUMO levels of P1–P3 were much lower than that of poly[2-methoxy-5-(2′-ethylhexoxy)-p-phenylenevinylene] (MEH-PPV) because of the electron-withdrawing characteristics of the pendant aromatic 1,3,4-oxadiazole groups. The luminance (5860 cd/m²) and current efficiency (1.45 cd/A) of an electroluminescence device [indium tin oxide/poly(3,4-ethylene dioxythiophene)/MEH-PPV/Al] were improved significantly to 16,261 cd/m² and 4.79 cd/A, respectively, through blending with P2 (50/50). This study suggests that copolymers P1–P3 are versatile materials for electron-transport/injection applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2259–2272, 2007