不同质子酸掺杂对银/聚苯胺纳米复合材料结构和导电性的影响

利用紫外光作为辅助条件,在反胶束体系中采用一步双原位法合成了硝酸(HNO3)、对甲基苯磺酸(TSA)和5-磺基水杨酸(SSA)掺杂的银/聚苯胺(Ag/PANI)纳米复合材料.通过对复合材料进行红外光谱(FTIR)、紫外光谱(UV-Vis)、扫描电镜(SEM)、X射线衍射(XRD)和导电性能的测试,研究了不同质子酸对Ag/PANI纳米复合材料结构、形貌和导电性能的影响.测试结果表明,3种酸掺杂制备的Ag/PANI纳米复合材料均为聚苯胺包覆银粒子的核-壳结构.不同的质子酸掺杂会对Ag/PANI纳米复合材料的电性能有重要影响.在3种酸掺杂的复合材料中,TSA掺杂的复合材料的电导率最佳,为215.14 S·cm-1.     

Synthesis,characterization and antibacterial properties of a novel nanocomposite based on polyaniline/polyvinyl alcohol/Ag

In this study, a novel nanocomposite based on polyaniline/polyvinyl alcohol/Ag (PANI/PVA/Ag) has been successfully synthesized. The chemical reduction method was used to produce Ag nanoparticle colloidal solution from Ag⁺ ions. The polymerization of aniline occurred in situ for the preparation of polyaniline (PANI) in the presence of ammonium persulfate. With exposure to Ag nanoparticles on the PANI/PVA composite, a new nanocomposite was obtained. The morphology and particle size of the novel nanocomposite was studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) analyses. According to XRD analysis, the size of nanoparticles was found to be in the range of 10–17 nm. SEM images showed the favored shape of nanoparticles as triangle which is a benign shape for antibacterial analysis. The antibacterial activity of the obtained nanocomposite was also evaluated against Gram positive bacteria Staphylococcus aureus (Staph. aureus) and Gram negative Escherichia coli (E. coli) using the paper disk diffusion method. The antibacterial study showed that the PANI/PVA composite did not have a very good antibacterial activity but PANI/PVA/Ag nanocomposites were found to be effective against two bacteria.     

一步法合成聚苯胺/十二烷基苯磺酸钠超疏水复合材料

在阴离子表面活性剂十二烷基苯磺酸钠(SDBS)体系中,采用一步法制得聚苯胺/SDBS超疏水复合材料.利用场发射扫描电子显微镜(FESEM)观察产物形貌并测定其元素组成.通过傅里叶变换红外光谱仪、紫外-可见光谱仪、X射线衍射等对其结构进行表征,用视频接触角测量仪测定材料的亲疏水性.考察SDBS浓度和溶液酸度对产物形貌及疏水性能的影响,探讨疏水机理.结果表明:在pH=1-9,SDBS浓度大于0.016 mol?L-1条件下,所制备复合材料的水接触角大于150°,SDBS掺杂使得苯胺单体的转化率高达98%.两亲分子SDBS亲水磺酸基与聚苯胺主链上的亚胺基不仅存在静电引力,而且能形成磺酰胺键,聚苯胺主链间又以氢键相互连接,SDBS分子的疏水烃基有序排列朝向聚苯胺主链外侧,从而组装形成具有微纳结构的聚苯胺/SDBS超疏水复合材料.本文结果有利于更好地理解聚苯胺/SDBS超疏水性复合材料的形成机理,对超疏水材料的设计提供新思路.     

Ag/PANI/Fe_2O_3复合纳米粒子的合成与催化性能

借助于PANI的还原性质,PANI/Fe2O3复合载体与AgNO3发生表面氧化还原反应,合成了Ag/PANI/Fe2O3复合纳米粒子。TEM和XRD结果表明,立方晶系纳米银的平均粒径10nm。FTIR结果表明,Ag与PANI及Fe2O3复合载体之间不存在化学键合作用,但由于PANI与Ag之间的电子相互作用,Ag/PANI/Fe2O3复合纳米粒子的FTIR吸收峰发生蓝移。Ag/PANI/Fe2O3复合纳米粒子对于间硝基苯磺酸钠的硼氢化钠还原反应表现出良好的催化活性,30min内间硝基苯磺酸钠的转化率达到86.77%。     

Reduction of silver nitrate by polyaniline nanotubes to produce silver-polyaniline composites

Polyaniline (PANI) nanotubes were prepared by oxidation of aniline in 0.4 M acetic acid. They were subsequently used as a reductant of silver nitrate in 1 M nitric acid, water or 1 M ammonium hydroxide at various molar ratios of silver nitrate to PANI. The resulting PANI-silver composites contained silver nanoparticles of 40–60 nm size along with macroscopic silver flakes. Under these experimental conditions, silver was always produced outside the PANI nanotubes. Changes in the molecular structure of PANI were analyzed by FTIR spectroscopy. Silver content in the composites was determined as a residue by thermogravimetric analysis, and confirmed by density measurements. The highest conductivity of a composite, 68.5 S cm⁻¹, was obtained at the nitrate to PANI molar ratio of 0.67 in water. Also, the best reaction yield was obtained in water. Reductions performed in an acidic medium gave products with conductivity of 10⁻⁴–10⁻² S cm⁻¹, whereas the reaction in alkaline solution yielded non-conducting products.     

Synthesis and characterization of C60/polyaniline composites from interfacial polymerization

C₆₀/polyaniline (PANI) nanocomposites have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in the presence of C₆₀ by using an interfacial reaction. When compared with the pure PANI nanofibers from the similar process, the diameter of the obtained C₆₀/PANI nanofibers was increased because of the encapsulation of C₆₀ into PANI during aniline polymerization, which resulted from the charge‐transfer interactions between C₆₀ and aniline fragment in PANI. In addition, the resulting C₆₀/PANI nanocomposites synthesized from the low initial C₆₀/aniline molar ratio (less than 1:25) showed the homogenous morphology composed of fiber network structures, which has an electrical conductivity as high as 1.1 × 10^?4 S/cm. However, the C₆₀/PANI nanocomposites from the higher initial C₆₀/aniline molar ratio (more than 1:15) showed the nonuniformly distributed morphology, and the electrical conductivity was decreased to 3.5 × 10^?5 S/cm. Moreover, the C₆₀/PANI nanocomposites from the interfacial reaction showed a higher value of electrical conductivity than the mechanically mixed C₆₀/PANI blends with the same C₆₀ content, because of the more evenly distributed microstructures. FTIR, UV–vis, and CV data confirmed the presence of C₆₀ and the significant charge‐transfer interactions in the resultant nanocomposites, which was responsible for the morphology development of the C₆₀/PANI and the variation of the electrical conductivity. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Hollow Ag/MnO2 Nanostructures with Controllable Shells: Synthesis and Oxygen Reduction Reaction Catalytic Performance

Novel hollow Ag/MnO₂ nanostructures with controlled shell composition and structure were designed and synthesized. In the present synthetic procedure, silver nanocrystals were oxidized by KMnO₄, and MnO₂ was heterogeneously formed on the surface of silver nanocrystals, then released Ag⁺ was photoreduced to silver adjacent to MnO₂. By simply changing the photoreduction moment, simultaneously with or after the addition of KMnO₄, hollow Ag/MnO₂ structures with different shell architectures—a monolayered shell composed of evenly mixed silver and MnO₂ and a double‐layered shell composed of an inner MnO₂ layer and an outer silver layer—can be obtained. Furthermore, the morphology of the hollow structure can be tuned by selecting different silver precursors, and the ratio of silver to MnO₂ in the shell can also be controlled by adjusting the ratio in the original reaction mixture. Electrochemical measurements revealed significantly enhanced catalytic performance in the oxygen reduction reaction for the prepared hollow structures. Compared with the Ag/MnO₂ composite, the onset potentials positively shift by about 50.0 mV and limiting current densities are nearly 2.0 times higher.     

Polyaniline-coated cellulose fibers decorated with silver nanoparticles

Cellulose fibers of 20 μm in diameter and aspect ratio of 2 or 10 were coated with protonated polyaniline (PANI) during the oxidation of aniline hydrochloride with ammonium peroxydisulfate in an aqueous medium. The presence of PANI has been proved by FTIR spectroscopy. The conductivity increased from 4.0 × 10⁻¹⁴ S cm⁻¹ to 0.41 S cm⁻¹ after coating the fibers with PANI. The percolation threshold in the mixture of original uncoated and PANI-coated fibers was reduced from 10 mass % PANI to 6 mass % PANI, as the aspect ratio changed from 2 to 10. The subsequent reaction with silver nitrate results in the decoration of PANI-coated cellulose fibers with silver nanoparticles of about 50 nm average size. The content of silver of up to 10.6 mass % was determined as a residue in thermogravimetric analysis. FTIR spectra suggest that the protonated emeraldine coating changed to the pernigraniline form during the latter process and, consequently, the conductivity of the composite was reduced to 4.1 × 10⁻⁴ S cm⁻¹, despite the presence of silver.     

三元复合材料PANI／Ag／MWNT的电化学行为和比电容

通过原位聚合的方式在银纳米粒子/多壁碳纳米管（Ag/MWCNT）复合材料的表面成功聚合苯胺单体制备了聚苯胺/银纳米粒子/多壁碳纳米管（PANI/Ag/MWCNT）三元复合材料苯．通过对三元复合材料的结构以及表面形貌进行分析,表明聚苯胺层完全包覆了Ag/MWCNT复合材料,形成了核壳式结构．同时银纳米粒子则以单质晶体的形态存在于多壁碳纳米管与聚苯胺层之间．三元复合材料电极在1 mol/L的KOH溶液中具有极低的阻抗,而与聚苯胺电极相比,这些复合材料电极则表现出更低的电阻、更高的电化学活性和更好的循环稳定性．尤其是当苯胺和Ag：MWCNTs质量比为5：5时,该复合材料电极在0.25 A/g的电流密度下表现出最大的比电容值为160 F/g．     

Ternary Ag/Polyaniline/Au nanocomposites: Preparation,characterization and electrochemical properties

Ternary Ag/Polyaniline/Au nanocomposites were synthesized successfully by immobilizing of Au nanoparticles (NPs) on the surface of Ag/Polyaniline (PANI) nanocomposites. Ag/PANI nanocomposites were prepared via in situ chemical polymerization of aniline in the presence of 4-aminothiophenol (4-ATP) capped silver colloidal NPs. Then, uniform gold (Au) NPs were assembled on the surface of resulted Ag/PANI nanocomposites through electrostatic interaction to get Ag/Polyaniline/Au nanocomposites. The nanocomposites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), ultraviolet visible spectroscopy (UV-Vis), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). Moreover, Ag/PANI/Au nanocomposites were immobilized on the surface of a glassy carbon electrode and showed enhanced electrocatalytic activity for the reduction of H₂O₂ compared with Ag/PANI.     

γ-Ray synthesis of starch-stabilized silver nanoparticles with antibacterial activities

Silver nanoparticles (Ag NPs) are fabricated through γ-irradiation reduction of silver ions in aqueous starch solutions. The UV–vis analyses show smaller sizes of Ag NPs produced, with higher yields, as the irradiation doses and/or Ag⁺ concentrations are increased. Higher concentrations of starch enhance the yields of Ag NPs, with no significant effects on their size. The most economical Ag NPs are produced at 5 kGy γ-irradiation of a 2×10⁻³ M solution of AgNO₃ containing 0.5% starch. They show a relatively narrow size distribution, indicated by TEM and its corresponding size distribution histogram. The XRD pattern confirms the face-centered cubic (fcc) Ag NPs embedded in starch molecules. Interactions between these nanoparticle surfaces and starch oxygen atoms are indicated by FT–IR. Antibacterial activities of Ag NPs against Escherichia coli appear dependent on the γ-ray doses applied.     

Preparation and characterization of polyaniline-containing Na-AlMCM-41 as composite material with semiconductor behavior

Composite material formed from a mesoporous aluminosilicate, Na-AlMCM-41, with conducting polyaniline (PANI) has been synthesized by an in situ polymerization technique. Studies of aniline adsorption over mesoporous Na-AlMCM-41 synthesized in our laboratory allowed us to find the modes in which aniline interacts with the active sites of Na-AlMCM-41. In order to obtain the best reaction conditions to polymerize aniline onto Na-AlMCM-41, aniline was first polymerized to produce pure PANI. Hence, the oxidative in situ polymerization was carried out by two procedures, differing in the polymerization time and in static or stirring conditions. Studies of infrared spectroscopy and UV-vis spectroscopy indicated that higher polymerization time and static conditions allowed us to obtain mainly polyaniline in emeraldine form on the host. The N(2) isotherm of the polyaniline/Na-AlMCM-41 composite (PANI/MCM) indicated that the shape was similar to that of MCM, but the shift to saturation transition to lower partial pressure shows that the channels are occupied by PANI and they are now narrowed. The thermal properties of PANI, Na-AlMCM-41, and composite were investigated by TGA analyses and we found that the polymer shows higher thermal stability when it is forming the composite. Scanning electron microscopy indicated that PANI is not on the outer surface of the host. Conductivity studies show that PANI/Na-AlMCM-41 exhibits semiconductor behavior at room temperature and its conductivity was 7.0 x 10(-5) S/cm, smaller than that of pure polyaniline. PANI/Na-AlMCM-41 conductivity shows an increase as temperature increases. Magnetic measurements at room temperature confirmed that the composite has paramagnetic behavior; at lower temperatures the composite became diamagnetic.     

γ-Ray irradiation as highly efficient approach for synthesis of supported high Pt loading cathode catalyst for application in direct methanol fuel cell

In this study, a γ-ray irradiation approach without addition of any commonly used reducing chemicals has been explored to synthesize carbon-supported high Pt loading (i.e., 80 wt.%) cathode catalyst for direct methanol fuel cell. Compared with the Pt catalyst prepared by impregnation-NaBH₄ reduction approach, the supported Pt catalyst synthesized by γ-ray irradiation has better dispersion of Pt nanoparticles on the carbon support with smaller particle size and narrower size distribution and has demonstrated enhanced catalytic activity toward oxygen reduction reaction and improved fuel cell performance.     

Graphene oxide‐induced polymerization and crystallization to produce highly conductive polyaniline/graphene oxide composite

Graphene oxide (GO)–polyaniline (PANI) composite is synthesized by in situ polymerization of aniline in the presence of GO as oxidant, resulting in highly crystalline and conductive composite. Fourier transform infrared spectrum confirms aniline polymerization in the presence of GO without using conventional oxidants. Scanning electron microscopic images show the formation of PANI nanofibers attached to GO sheets. X‐ray diffraction (XRD) patterns indicate the presence of highly crystalline PANI. The sharp peaks in XRD pattern suggest GO sheets not only play an important role in the polymerization of aniline but also in inducing highly crystalline phase of PANI in the final composite. Electrical conductivity of doped GO–PANI composite is 582.73 S m^?1, compared with 20.3 S m^?1 for GO–PANI obtained by ammonium persulfate assisted polymerization. The higher conductivity appears to be the result of higher crystallinity and/or chemical grafting of PANI to GO, which creates common conjugated paths between GO and PANI. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1545–1554     

Synthesis of a new electrically conducting nanosized Ag–polyaniline–silica complex using γ-radiolysis and its biosensing application

In this study, a new electrically conducting nanosized Ag–PANI–silica complex, in which nano-silver is bound to silica and polyaniline (PANI), has been synthesized by using γ-irradiation at room temperature and not by using polyvinylpyrrolidone (PVP) as a colloidal stabilizer. The conductivity of nanosized Ag–PANI–silica complex was determined by using the Van der PauW method, and the complex turned out to have a high semi-conductivity (200 S/cm). The optical property and morphology were characterized by using a UV–vis spectrophotometer, field emission-scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The optical absorption bands of UV–vis analysis revealed a peak at 262, 368, and a slowly decreasing band at 600–800 nm originating from the a nanosized Ag–PANI–silica complex. FE-SEM and TEM showed that the nanosized Ag–PANI–silica complex has a particle size ranging from 10 to 30 nm and high stability. The nano-complex prepared by γ-irradiation can be applicable to be used as biosensor materials.     

Conductive elastomeric nanocomposites based on oxidation of aniline with silver nitrate via inverse emulsion polymerization

The present investigation describes a facile and rapid approach of conductive nanocomposites production and assesses the opportunity of their use as electro‐mechanical sensors. Hybrid materials containing silver and polyaniline nanoparticles reinforcing a thermoplastic elastomeric matrix were studied. The approach developed includes ultrasonically assisted in situ inverse emulsion polymerization of aniline oxidized by a weak oxidant and silver nitrate, and supported with a strong oxidant, ammonia peroxydisulfate. Aniline was doped with dodecylbenzene sulfonic acid in the presence of dissolved styrene–isoprene–styrene thermoplastic elastomer. While conventional polymerization of aniline with silver nitrate takes 2 weeks, by utilization of inverse emulsion polymerization, the reaction time reduces to 5 days. The assistance of a strong oxidant dramatically shortens the reaction time to 30 min. The technique developed results in uniform distribution of polyaniline/silver (PANI/Ag) conductive nanoparticles in the elastomeric matrix. The morphological studies of the films reveal spherically shaped 45 nm Ag particles. The presence of PANI/Ag in the styrene–isoprene–styrene elastomeric matrix enhances the electrical, thermal, and mechanical properties of the nanocomposites. The approach described provides an opportunity of the development of tunable structures and a remarkably distinctive architecture. A rapid electrical resistance response to an applied strain makes the nanocomposites developed useful as sensitive strain sensors. Copyright © 2014 John Wiley & Sons, Ltd.     

APS/NaClO 复合氧化剂对乳液法合成聚苯胺的微观形貌及其电化学性能的影响

采用乳液法, 以过硫酸铵(APS)和次氯酸钠(NaClO)为复合氧化剂合成导电聚苯胺(PANI). 考察了NaClO 的加入与否对PANI 微观形貌与电化学性能(循环伏安和电导率)的影响, 以及APS、乳化剂十二烷基苯磺酸钠(SDBS)和NaClO的用量对PANI 电化学性能的影响. 结果表明: NaClO 的加入对PANI 的微观取向结构具有重要的影响. 与采用单一APS 合成的PANI 相比, 复合氧化剂合成的PANI 具有较高的循环伏安峰电流以及更加优异的电导率(约为前者的2.6倍). 当苯胺(An)与APS 的物质的量比(n_An:n_APS )为8:7, An 与SDBS 的物质的量比(n_An:n_SDBS )为10:4, NaClO 用量为5%(质量分数)时, PANI 的各项性能指标达到最好; 紫外可见光谱和红外光谱的表征结果表明, 采用复合氧化剂并未对PANI 的分子结构产生明显的影响.     

Matrix dependence of the conformations of the 1,4-diethylbenzene radical cation at low temperatures

1,4-Diethylbenzene radical cation generated in six different halocarbon matrices by ⁶⁰Co γ-ray irradiation has been studied by ESR at low temperatures. The spectra exhibit drastic variations in different matrices, showing that the conformation of the radical cation is largely dependent on the matrix.     

Study of the isomeric ratios in 107Ag(γ, n)106m,gAg reaction of natural silver induced by bremsstrahlungs with endpoint energies in the giant dipole resonance region

We measured for the first time the isomeric ratios in ¹⁰⁷Ag(γ, n)^106m,gAg reaction by using the activation method and γ-ray spectroscopic method for the whole giant dipole resonance region. The high-purity natural Ag foils in disc shape were irradiated with bremsstrahlungs generated from an electron accelerator Microtron. The induced gamma spectra in the irradiated foils were measured by the high resolution γ-ray spectroscopic system which consists of a high-purity germanium detector and a multichannel analyzer. In order to improve the accuracy of the experimental results, necessary corrections were made in the γ-ray activity measurements and data analysis. The results were analyzed, discussed and compared with those of other authors. For the above mentioned reaction, the isomeric ratios in the energy range from 14 to 24 MeV bremsstrahlungs in this work (except the values at 14, 18 and 20) are new measurements.     

Ag／TiO2复合纳米催化剂的制备和表征及其光催化活性

 采用光还原沉积贵金属法，制备了Ag／TiO2复合纳米催化剂．通过调节溶液的pH值控制TiO2表面负载银的形貌，利用AAS，XRD，TEM和XPS等手段对样品进行了表征．以苯胺氧化为模型反应，考察了Ag／TiO2复合纳米催化剂样品的光催化活性以及银沉积量和沉积形貌对催化剂活性的影响．结果表明，通过调控光还原沉积条件，可在平均粒径为24nm左右的TiO2颗粒上获得3nm左右均匀分散的银粒子；在TiO2上沉积适量的具有较高分散度的金属Ag，能有效提高TiO2对苯胺氧化反应的光催化活性．