PAN/PANI/rGO/Au复合纤维的制备及其催化、原位SERS监测性能

本研究首先利用静电纺丝技术构建了还原氧化石墨烯(rGO)增强的聚丙烯腈/聚苯胺复合纤维(PAN/PANI/rGO),然后采用原位还原的方法在其表面生长金纳米颗粒得到了PAN/PANI/rGO/Au复合纤维,通过SEM,FTIR,XRD,XPS,Raman和UV-Vis光谱等手段对复合纤维进行了结构和形貌表征,最后以NaBH4还原四硝基苯酚(4-NP)为模型,研究了复合纤维的催化性能和原位SERS检测该催化还原反应的过程,并将其与同种方法制备的PAN/PANI/GO/Au和PAN/PANI/Au复合纤维进行比较。结果表明,rGO增强的PAN/PANI/rGO/Au复合纤维具有优于PAN/PANI/GO/Au和PAN/PANI/Au复合纤维的催化活性、原位增强SERS检测的能力和循环性能。     

阴极气体O2对石墨烯/聚苯胺/不锈钢双极板耐蚀性的影响

目的 提高质子交换膜燃料电池(PEMFC)双极板的耐腐蚀性能。方法 采用循环伏安法(CV)在316L不锈钢(SS)基材上制备还原氧化石墨烯(rGO)/聚苯胺(PANI)层-层复合双极板。用透射电镜(TEM)和扫描电镜(SEM)进行形貌观察,用红外光谱(FTIR)和拉曼光谱(Raman)确定官能团结构,用紫外可见光谱(UV-vis)确定分子共轭状态,用X射线光电子能谱(XPS)确定化学成分和键合状态。在模拟PEMFC阴极工作环境下研究rGO/PANI/316L SS层-层复合双极板的耐腐蚀性能,向体系中通入氧气(O₂),测量开路电位(OCP)、电化学阻抗谱(EIS)和极化曲线评价双极板的抗腐蚀性能。结果 在离子液体1-乙基-3-甲基咪唑硫酸甲酯中,通过电聚合能够获得厚度为53μm的PANI膜层,在pH=4的0.03 mol/L K₂SO₄溶液中还原氧化石墨烯(GO),在PANI上获得厚度为10μm的rGO膜层。PANI呈中间氧化态,sp2杂化的r GO和PANI之间的相互作用使得共轭效应增强。连续致密的rGO覆盖在多孔的P...     

富氧条件下烃类选择性催化还原NO用纳米贵金属催化剂的研究进展

纳米贵金属系列催化剂以其特有的性能得到广泛研究.本文对纳米贵金属催化剂（Pt、Pd、Rh、Ag、Ir、Au）在富氧条件下进行烃类选择性催化还原NO的性能、特点以及存在的问题进行了分析,介绍了复合贵金属催化剂体系及其反应机理,提出了对进一步改善纳米贵金属催化剂性能的途径.     

Ag2S/rGO纳米复合材料的细菌还原制备及光电性能研究

以一种革兰氏阴性菌(S. oneidensis MR-1)为生物还原剂,Na2S2O3为电子受体,在氧化石墨烯(GO)表面原位合成了Ag2S/rGO纳米复合材料,对其进行了表征和光电性能测试。结果表明,细菌还原得到粒径约10 nm的Ag2S纳米粒子,均匀分布在还原氧化石墨烯(rGO)上;光电性能测试表明,与纯Ag2S相比,Ag2S/rGO纳米复合材料电极的光电流密度约提高了3倍,光生电子-空穴对的分离效率更高,表现出更加优异的光电化学性能。     

飞机结构铝合金PPy/rGO复合镀层及其防腐蚀性能

为研究氧化石墨烯（GO）与聚吡咯（PPy）复合镀层的防腐性能,采用恒电位法在铝合金片上电化学聚合吡咯单体,形成PPy镀层,再在PPy镀层表面电镀GO形成聚吡咯/还原氧化石墨烯（PPy/rGO）复合镀层。采用SEM、Raman以及FTIR对镀层的微观形貌与结构成分进行表征,采用接触角测量仪测试镀层的疏水性能,通过极化曲线、电化学阻抗谱（EIS）分析镀层的防腐蚀性能。结果表明：PPy/rGO复合镀层表面的rGO镀层覆盖PPy镀层表面的针孔、凹槽等缺陷,使复合镀层表面光滑、平整,屏蔽性能增强;疏水性能也得到提高。PPy/rGO复合镀层腐蚀电流密度比PPy镀层、铝合金小,表明其腐蚀速率低。PPy/rGO复合镀层比PPy镀层与铝合金拥有更大的阻抗弧,说明PPy/rGO复合镀层对溶液中电解质离子有更强的阻碍作用。铝合金和PPy镀层出现不同程度的腐蚀现象,而PPy/rGO复合镀层并未发生明显的腐蚀现象,说明PPy/rGO复合镀层防腐蚀性能更好。     

聚苯胺原位聚合改性氧化石墨烯制备复合涂层及其耐腐蚀性能研究

目的 提高聚苯胺(PANI)涂层的腐蚀防护性能,并明确其防腐机理.方法 通过原位聚合的方法,采用PANI对氧化石墨烯(GO)进行功能化修饰,并对其在GO表面的生长状态进行调控.利用傅里叶变换红外光谱仪(FTIR)、X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、拉曼光谱仪(Raman)和场发射高分辨扫描电镜(FESEM),对功能化GO的结构和形貌进行表征和分析;然后将其引入到聚苯胺涂层中,制备PANI/GO复合涂层.采用电化学阻抗谱(EIS)详细研究PANI涂层以及不同的PANI/GO复合涂层对不锈钢基材的腐蚀防护效应,并对其耐腐蚀机制进行探讨.结果 PANI均匀地生长在GO片层上,其结构与形貌可以通过控制苯胺的添加量进行有效调控,且PANI的原位聚合促进了GO的片层剥离及舒展,改善了其分散性以及与涂层间的相容性.与单一PANI涂层相比,PANI/GO复合涂层的稳定开路电压值较大,且当苯胺与GO的质量比为5︰1时,获得的功能化GO的分散效果最佳,对聚苯胺涂层的腐蚀防护性能增强效果最为显著.此时复合涂层表现出最大的容抗弧直径,且电化学阻抗谱拟合后的电荷转移电阻最大,双电层电容最小.结论 PANI涂层本身可以在金属表面形成具有屏蔽作用的保护层,但其非致密的形态结构及腐蚀环境下的分子构型变化损害了涂层的腐蚀防护性能.通过功能结构化GO的复合,尤其是在GO分散性最佳的状态下,可有效提高涂层的致密性和抗渗透性,并且可抑制因质子反应导致的分子构型变化对涂层结构的破坏,从而增强涂层的腐蚀防护性能.     

不同壳层厚度Au@SiO_2的表面增强拉曼效应

通过电偶置换反应制备了尺寸在30~35 nm的结晶性良好的Au纳米颗粒,并成功在其表面包覆了不同厚度的Si O2壳层,利用TEM、HRTEM和UV-Vis对样品的结构和形貌进行了表征,并以罗丹明6G(R6G)为探针分子,对Au@SiO_2复合粒子的表面增强拉曼散射(SERS)效应进行了研究。结果显示,相对于Au纳米颗粒,Au@SiO_2复合粒子显著提高了拉曼信号的质量和检测的灵敏度,且Si O2壳层厚度对其SRES效应影响显著,壳层厚度为2 nm的复合粒子对R6G分子的检测极限可达10~(-7)mol/L。     

不锈钢表面聚苯胺基复合涂层的制备与防腐蚀性能研究

目的 制备一种新型复合防腐涂层,增强316L不锈钢在中高温硫酸溶液中的耐蚀性.方法 首先使用化学氧化法在石墨(G)颗粒表面原位聚合聚苯胺(PANI),制得PANI/G复合材料,再使用环氧树脂(EP)作为粘结剂,制备PANI/G/EP复合涂层.对比了PANI/G/EP复合涂层与PANI/EP复合涂层及添加氧化石墨烯(GO...     

PANI/Ag-TiO2纳米纤维复合材料的制备及其抗菌性能研究

采用水热法制备Ag掺杂量不同的Ag/TiO2纳米复合材料,通过原位聚合法制备PANI/Ag-TiO2纳米纤维复合材料,利用XRD、SEM、FT-IR等检测技术对复合材料的结构进行了表征。研究了光源、Ag掺杂量、不同实验菌种等因素对PANI/Ag-TiO2纳米纤维复合材料抗菌性能的影响。结果表明：在无光照射情况下,PANI/Ag-TiO2纳米纤维复合材料具有良好的抗菌性能,在长波紫外光照射情况下,抗菌性能进一步增强。在浓度1 mg/mL时,在无需光照的情况下对4种实验菌种杀菌率均达到99.99%。     

石墨烯/铜复合材料的制备与摩擦性能测试

以化学镀结合粉末冶金法制备石墨烯/铜基复合材料(Cu@r GO/Cu)。为了改善石墨烯(r GO)在铜基体中的分散性以及两者之间的可润湿程度,首先采用化学镀工艺制备镀铜石墨烯(Cu@r GO),并通过SEM和XRD对镀层形貌和物相组成进行检测分析。为了检验Cu@r GO/Cu复合材料的摩擦性能,对Cu@r GO/Cu复合材料摩擦性质进行测试。结果表明:Cu@r GO表面均匀镀覆一层铜并附着粒径约为50 nm的纳米铜颗粒,rGO的褶皱结构以及化学镀的预处理过程有利于纳米铜颗粒长大。呈网状结构的镀铜rGO可以很好的释放掉因摩擦而产生的应力集中,形成C—Cu力转移体系,保护摩擦表面;同时散落在r GO表面的纳米铜颗粒,在摩擦过程中类似于许多"滚动轴承",有效地改善复合材料的摩擦性能。     

Fabrication and characteristics of spindle Fe2O3@Au core/shell particles

The fabrication and characteristics of spindle Fe2O3@Au core/shell particle were investigated, and the effect of the core/shell nanoparticles as the surface enhanced Raman spectroscopy (SERS)-active substrates was studied. By using the seed-catalyzed reduction technique, anisotropic Fe2O3@Au core/shell particles with spindle morphology were successfully prepared. The Fe2O3 particles with spindle morphology were initially prepared as original cores. The Au nanoparticles of 2 nm were attached onto the Fe2O3 particles through organosilane molecules. Uniform Au shell formed onto Fe2O3 core modified by Au nanoparticles through the in-situ reduction of HAuCl4. The shell thickness was controlled through regulating the concentration of HAuCl4 solution. The results of TEM, XRD and UV-vis characterization show that the core/shell particles with the original shape of the Fe2O3 particles are obtained and these surfaces are covered by Au shell completely. The surface enhanced Raman spectrum of the probe molecules adsorbed on these core/shell substrates is strong and the intensity is enhanced with the increase of the thickness of Au shell or the aspect ratio of particles. The spindle Fe2O3@Au core/shell particles exhibit optimum (SERS) activity.     

Synthesis and Characterization of Reduced Graphene Oxide- Polyaniline Composite for Supercapacitor Applications

Graphene oxide (GO) is synthesized from commercially available graphite powder. The prepared GO is converted to reduced graphene oxide (rGO) by chemical reduction using sodium borohydride and sodium hydroxide. The rGO is characterized via X-ray diffraction, Raman spectroscopy and scanning electron microscopy. Conducting polymer–polyaniline, was prepared by oxidative polymerization in an electrolyte- hydrochloric acid and using ammonium persulphate as oxidant. The structure and doping of polyaniline were studied by Fourier-transform infrared spectroscopy and ultra-violet visible spectroscopy. To enhance the conductivity of the rGO, the conducting polymer mixed with rGO and rGO/Conducting polymer composites were prepared. The composite was characterized by cyclic voltammetry, AC impedance spectroscopy. A symmetrical supercapacitor (SC) has been fabricated based on rGO/PANI composites. The prepared composites were shown specific capacitance of 72 F g^–1 at 2 mV s^–1.     

SERS,FT-IR and photoluminescence studies on single-walled carbon nanotubes/conducting polymers composites

Surface-enhanced Raman scattering (SERS), Fourier transform infrared (FT-IR) and photoluminescence (PL) spectroscopies were used to investigate composites based on single-walled carbon nanotubes (SWNTs) and different conducting polymers like polyaniline (PANI), poly-paraphenylene vinylene (PPV) and poly 3-hexylthiophene (3-PHT). In the case of SWNTs/PANI, different composites are obtained by adding dispersed SWNTs powder to the polymer solutions and by chemical polymerization of aniline in presence of SWNTs. The difference originates in the irreversible chemical transformation of SWNTs in the polymerization medium. The synthesis medium used for the preparation of PANI transforms SWNTs in fragments of shorter length like closed-shell fullerenes. This explains the similarity of SERS and FT-IR spectra of the composites PANI/SWNTs and PANI/C₆₀, chemically synthesized. Electrochemical polymerization of aniline in an HCl solution on a SWNT film leads to a covalent functionalization of SWNTs with PANI. In this case, Raman scattering data suggest an additional nanotubes roping with PANI as a binding agent. A post treatment with the NH₄OH solution of polymer-functionalized SWNTs involves an internal redox reaction between PANI and carbon nanotubes. As a result, the polymer chain undergoes a transition from the semi-oxidized state into a reduced one. In the case of PPV and 3-PHT, the effect of the concentration of SWNTs on the photoluminescence properties will be described and compared, as probes of interaction.     

Preparation,FTIR spectroscopic characterization and isothermal stability of differently doped conductive fibers based on polyaniline and polyacrylonitrile

Conductive fibers based on polyaniline (PANI) and polyacrylonitrile (PAN) were obtained by stirring with magnetic bar. This research was conducted to investigate conducting fibers of polyaniline:polyacrylonitrile (PANI:PAN) composite with different weight ratios of aniline in PAN matrix. The fibers were prepared by stirring process. The best conductivity behavior of the fibers was obtained with 5 mL of aniline. The fibers obtained were characterized using Fourier-transform infrared spectra (FTIR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The variation of electrical conductivity with different type doping agents (HCl, H₂SO₄ and HClO₄) and the stability in terms of DC electrical conductivity retention was studied in an oxidative environment by isothermal characteristics.     

Structural properties of some conducting polymers and carbon nanotubes investigated by SERS spectroscopy

In this paper, we present Surface Enhanced Raman Scattering (SERS) experiments performed successfully on some conducting polymers and carbon nanotubes deposited in thin films on rough metallic surfaces. The enhancement mechanism in SERS has a twofold origin: electromagnetic and chemical. The electromagnetic enhancement is, however, the dominant mechanism and consists in the excitation of localized and delocalized surface plasmons (SP). The second enhancing mechanism for SERS, not yet convincingly supported by experimental data, is of chemical origin. This mechanism is due to the increase of the polarizability of the molecules on the metal surface under the action of the incident radiation, leading to the formation of new chemical bonds between the molecules and the metal surface. Unfortunately, the experimental data available to argue the presence of a chemical process are scarce and scattered. In this paper, we try to present some details regarding this aspect. In order to do so, we studied poly 3-hexylthiophene (3-PHT) and polyaniline (PAN) as a function of the type of the rough metallic support (Ag, Au or Cu), the oxidization state and thickness of the polymer layer. We studied also carbon single walled nanotubes. Our experiments reveal the existence of a chemical surface effect. The results obtained for 3-PHT show that SERS spectra depend on the oxidizing properties of the metal surface and on the nature of the solvent. This dependence is explained by the existence of some interfacial reactions that lead to the formation of interface compounds. The SERS measurements reported here reveal an increase of the intensities of the Raman lines, accompanied by a modification of the corresponding intensity ratios, when the degree of doping is increased. We observe for the first time by SERS spectroscopy that doping of 3-PHT with FeCl₃ leads to the appearance of a state of disorder in the structure of the macromolecular chain, as a result of steric hindrance effects. The type of the rough metallic support can modify SERS spectra and such an effect is clearly shown for the polyaniline case. No such dependence on metallic support type is observed on the SERS spectra of carbon nanotubes.     

Gold/oxide heterostructured nanoparticles for enhanced SERS sensitivity and reproducibility

In surface-enhanced Raman scattering(SERS),it is highly desirable to obtain Raman signals with high sensitivity and reproducibility from noble metal nanoparticle substrates,which remains a great challenge due to the inhomogeneity of the plasmonic coupling that is sensitive to the interparticle nanogaps.In this work,we report that the interparticle plasmonic coupling could be circumvented by first synthesizing Au/metal or nonmetal oxide heterostructured nanoparticles and then depositing them uniformly onto the substrates,leading to high reproducibility of the Raman signals.Strong plasmonic coupling has been found at the Au/oxide interface,which enables high sensitivity of the SERS analysis that accompanies the excellent signal reproducibility.Among different oxides investigated(SiO_2,TiO_2 and Fe_2O_3),the Au/Fe_2O_3 heterostructured nanoparticles demonstrate the highest Raman enhancement effect.We believe our strategy opens a promising route to fabricate SERS substrates that are capable of sensitively and quantitatively detecting molecules of interest in a much reliable manner.     

一种中空金/银双金属纳米颗粒的制备及其SERS性能

以银纳米颗粒为牺牲模板,利用Ag和HAu Cl4之间的置换反应,结合柠檬酸钠同步还原的方法制备了一种中空金/银双金属纳米颗粒。通过对颗粒形貌及局域表面等离子体共振(LSPR)的分析,初步研究了此类金/银纳米颗粒的生长机理,并对影响反应的因素进行了探讨。结果表明,通过控制反应条件可以实现对LSPR的精密调控。该类金/银双金属纳米颗粒可用作为SERS基底,苯硫酚在其表面增强因子可达107,并具有良好的信号重现性。该基底用于atto610标记的生物素与亲和素的SERS检测,检测限可达80 pg/m L。     

A novel formation process of polyaniline micro-/nanofiber network on solid substrates

By a chemical oxidative polymerization of aniline on solid substrates treated with Au nanoparticles (Au-NPs) deposition and 4-aminothiophenol (ATP) modification, polyaniline (PANI) fibers were obtained in micro-/nanosize with two-dimensional network structures. The observation by laser scanning microscopy (LSM) indicated that the formation of PANI fibrous network occurred during the drying process rather than the polymerization. It was suggested the ATP modification on Au-NPs deposited substrate resulted in an inhomogeneous grafting of solution-formed PANI on the solid substrates, which self-aggregated to the fibrous network structure with the evaporation of water due to interchain interactions. The influence of polymerization conditions on the formation of fibrous network and the conducting property of the prepared film were discussed. Results from the gas sensing of the as-prepared PANI sensor upon exposure to NH₃ confirmed that the sensitivity and responding rapidity was improved greatly by the PANI 2D fibrous network structure. Especially, a rapid response in resistance change on NH₃ with low concentration indicated that the developed method in this work can be used to fabricate highly sensitive PANI gas sensors.     

Au/Ni双金属纳米颗粒的制备及其催化制氢活性

采用化学共还原法制备了聚乙烯吡咯烷酮(PVP)保护的Au/Ni双金属纳米颗粒,采用UV-Vis、TEM对所合成的纳米颗粒进行了表征,研究了双金属纳米颗粒的化学组成对其催化水解Na BH4制氢活性的影响。结果表明:所制备的Au/Ni双金属纳米颗粒的平均粒径为2.9~4.2 nm,Au/Ni双金属纳米颗粒的催化活性高于Au和Ni单金属纳米颗粒的活性,Au50Ni50双金属纳米颗粒的催化活性最高,30℃时其催化活性数值达到550 mol-H2·h-1·mol-M-1。XPS和密度泛函理论(DFT)的结果都表明:Au/Ni双金属纳米颗粒优异的催化性能可归因于电荷转移效应,Ni原子与Au原子之间发生的电子转移使得Au原子带负电而Ni原子带正电,荷电的Au和Ni原子成为催化反应的活性中心。Au50Ni50双金属纳米颗粒催化水解Na BH4制氢的活化能为61.9 k J/mol。     

CC/PANI/TiO2复合材料的制备及其光催化性能研究

先采用原位聚合的方法在碳布上负载聚苯胺,然后利用溶剂热法在制备的碳布/聚苯胺(CC/PANI)复合材料上生长二氧化钛纳米片,得到了可便捷分离的CC/PANI/TiO₂复合光催化材料。通过SEM、XRD、UV、FTIR、XPS等手段对所制备的样品进行了形貌和结构表征,并比较了CC/PANI/TiO₂复合材料和纯TiO₂紫外-可见光条件下催化降解RhB的活性差异,结果表明CC/PANI/TiO₂复合材料具有比TiO₂更优异的光催化活性。光致发光光谱说明CC/PANI/TiO₂复合材料的发光强度比纯TiO₂的弱,有效抑制了光生载流子的复合;瞬态光电流响应和电化学阻抗谱(EIS)证明CC/PANI/TiO₂纳米复合材料更有效促进电子-空穴对分离和提高转移效率;活性物质捕捉实验证实?OH和?O_2^-是复合材料光催化降解RhB过程中的主要活性物质。CC/PANI/TiO₂复合材料循环利用6次后,仍然具有较高的催化活性,显示了其在污水处理领域中的良好应用前景。