Synthesis of polyaniline/mesoporous carbon nanocomposites and their application for CO<Subscript>2</Subscript> sorption

Ordered mesoporous carbons (OMC), were synthesized by nanocasting using ordered mesoporous silica as hard templates. Ordered mesoporous carbons CMK-1 and CMK-3 were prepared from MCM-48 and SBA-15 materials with pore diameters of 3.4 nm and 4.2 nm, respectively. Mesoporous carbons can be effectively modified for CO₂ adsorption with amine functional groups due to their high affinity for CO₂. Polyaniline (PANI)/mesoporous carbon nanocomposites were synthesized from in-situ polymerization by dissolving OMC in aniline monomer. The polymerization of aniline molecules inside the mesochannels of mesoporous carbons has been performed by ammonium persulfate. The nanocomposition, morphology, and structure of the nanocomposite were investigated by nitrogen adsorption-desorption isotherms, Fourier Transform Infrared (FT–IR), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and thermo gravimetric analysis (TGA). CO₂ uptake capacity of the mesoporous carbon materials was obtained by a gravimetric adsorption apparatus for the pressure range from 1 to 5 bar and in the temperature range of 298 to 348 K. CMK-3/PANI exhibited higher CO₂ capture capacity than CMK-1/PANI owing to its larger pore size that accommodates more amine groups inside the pore structure, and the mesoporosity also can facilitate dispersion of PANI molecules inside the pore channels. Moreover, the mechanism of CO₂ adsorption involving amine groups is investigated. The results show that at elevated temperature, PANI/mesoporous carbon nanocomposites have a negligible CO₂ adsorption capacity due to weak chemical interactions with the carbon nanocomposite surface.     

Mesoporous silica supports for improved thermal stability in supported Au catalysts

In this work, we present a comprehensive review of our research on the role of mesoporous silica pore architecture, composition of the pore walls (addition of Co or Al), and silica surface chemistry (surface modification by TiO₂) to improve the hydrothermal stability of Au particles. We have found that mesoporous silica architecture plays an important role in improving Au stability, with three dimensional mesoporous architectures being less effective than one dimensional (1-D) pores. The tortuous 1-D pores in aerosol silica were found to be most effective at controlling Au particle size. Since Au particles continue to grow larger than the pore diameter, we conclude that Ostwald ripening must be the dominant sintering pathway for these Au catalysts. These catalysts are active for CO oxidation even after the Au particles have grown large enough to block the pores, suggesting that the thin walls of mesoporous silica provide easy access to gas phase molecules. Further improvements in Au stability and reactivity were obtained by surface modification of the aerosol and MCM-41 silica with TiO₂. After TiO₂ modification of the silica, the Au particles remained smaller than the pore size (< 3 nm) even after three cycles of CO oxidation at temperatures up to 400 °C.     

High performance nanocomposite electrodes of mesoporous silica platelet‐polyaniline synthesized via impregnation polymerization

A novel high specific capacitance mesoporous polyaniline (PANI)/silica platelet nanocomposite electrode material for supercapacitors was prepared by an impregnation polymerization. The initiator was embedded firstly in the mesoporous silica pores and channels and then initiated the polymerization of aniline (AN). Compared with the other mesoporous silica materials, the mesoporous silica platelets possess a relative shorter mesoporous channels, leading an easier penetration process of initiator and AN to the inner of mesoporous silica platelets. The structures, morphologies, and electrochemical properties of the nanocomposites were thoroughly studied by a series of methods, such as X‐ray diffractometry, scanning electron microscope, nitrogen adsorption‐desorption tests, infrared spectroscopy, thermogravimetric analysis, and electrochemical measurements. The results revealed that the PANI existed both in the inner and surface of the mesoporous silica platelets, leading a continual conductive network and a large specific surface area. These features provide the nanocomposites an excellent electrochemical performance. The biggest specific capacitance is 1,598 F g⁻¹ at a current density of 0.5 A g⁻¹. POLYM. COMPOS., 38:1616–1623, 2017. © 2015 Society of Plastics Engineers     

Enhanced electrochemical properties of polyaniline-coated multiwall carbon nanotubes

MWNT (multiwall carbon nanotubes) was coated by using in-situ chemical polymerization of aniline monomer. Structure characterizations, such as N₂ adsorption analysis and transmission electron microscopy, demonstrate that a thin layer of PANI (polyaniline) is well coated on the pore surface of MWNT. As evidenced by constant current charge-discharge test, specific capacitance of PANI-coated MWNT increases by a factor of 5 due to the incorporation of PANI onto the pore surface of MWNT. However, the capacitive behavior deteriorated due to the narrower pore size and extra faradiac resistance derived from PANI.     

原位聚合沉积透明导电聚苯胺薄膜的研究进展

苯胺在化学氧化聚合过程中,可自发地聚合沉积在不同基体表面,形成透明导电聚苯胺薄膜。重点介绍近年来国内外在玻璃、聚合物、纤维织物和二氧化硅基体表面原位聚合沉积透明导电聚苯胺薄膜的研究进展,并探讨了反应机理。展望了透明导电聚苯胺薄膜在光电器件和微电子器件领域的应用前景。     

Octadecyl grafted MCM-41 silica spheres using trifunctionalsilane precursors – preparation and characterization

MCM-41 silica spheres were prepared via the pseudomorphic route. Subsequent surface modification of the mesoporous silica spheres was achieved by two silylating agents, n-octadecyltrihydridosilane and n-octadecyltrimethoxysilane, which provided different surface coverages. The MCM-41 pore structure, surface properties and morphological features were examined by small angle X-ray scattering, nitrogen adsorption–desorption and scanning electron microscopy. The investigations revealed an influence of the silica source on the mesoporous structure, as reflected by a higher long-range order for the pores in MCM-41 spheres prepared from Kromasil silica. Surface modification is accompanied by a reduction of the surface area, pore diameter and pore volume of the MCM-41 materials, whereas the spherical morphology of the spheres is retained. The degree of grafting and cross-linking of the alkylsilanes was determined by ²⁹Si NMR spectroscopy. A higher degree of alkyl chain grafting was observed for the solvent extracted MCM-41 spheres and for samples prepared via surface polymerization.FTIR and ¹³C NMR spectroscopies were employed to study the conformational behaviour and mobility of the grafted octadecyl chains. The conformational order was found to strongly depend on the history of the MCM-41 supports (calcination, solvent extraction) and on the actual surface modification procedure. In general, a lower conformational order was observed for the present mesoporous alkyl modified silica spheres as compared to conventional C₁₈ modified silica gels which is mainly attributed to the lower surface coverage.     

Preparation of Mesoporous Carbons from Acrylonitrile-methyl Methacrylate Copolymer/Silica Nanocomposites Synthesized by in-situ Emulsion Polymerization

Acrylonitrile-methyl methacrylate (AN-MMA) copolymer/silica nanocomposites were synthesized by in-situ emulsion polymerization initiated by 2,2'-azobis(2-amidinopropane) dihydrochloride absorbed onto colloidal silica particles, and the mesoporous carbon materials were prepared through carbonization of the obtained AN-MMA copolymer/silica nanocomposites, followed by HF etching. Thermogravimetric analysis of AN-MMA copolymer/silica nanocomposites showed that the carbon yield of copolymer was slightly decreased as silica particle incorporated. N₂ adsorption-desorption, scan electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the mesoporous carbon materials. Both SEM and TEM results showed that disordered mesopores were formed in the obtained carbon material mainly through templating effect of silica nanoparticles. The diameter of mesopores was mainly distributed in the range from 5 nm to 15 nm. The mean pore diameter and total pore volume of the material increased as the mass fraction of silica in the nanocomposites increased from 0 to 24.93%. The significant increase of the mean pore diameter and the decrease of surface area for the carbon material prepared from the nanocomposite with 24.93% silica were caused by partial aggregation of silica nanoparticles in the polymer matrix.     

多功能性聚苯胺/聚合物纳米复合材料的制备及应用

基于国内外最新研究文献及本课题组的研究,综述了多功能性聚苯胺/聚合物纳米复合材料的制备方法、性能及应用前景。聚苯胺/聚合物纳米复合材料可以由机械共混法、涂布法和原位聚合法,如分散聚合法、模板诱导聚合法及电化学聚合法制备得到。聚苯胺/聚合物纳米复合材料在透明导电塑料薄膜、防静电涂料、导电纤维、电致发光器件、电磁屏蔽材料等领域有着广阔的应用前景。     

Effects of mesoporous silica particles on the emulsion polymerization of methyl methacrylate

Rod‐like and spherical mesoporous SBA‐15 silica particles were synthesized as pure silicas and surface modified by organosilane coupling agents firstly, and then the effects of these mesoporous materials on the critical micelle concentration (CMC) of sodium dodecylsulfate (SDS), the stabilities of batch and semi‐continuous MMA emulsion polymerizations, and the molecular weights and molecular weight distributions of the polymer products were studied. The incorporation of both unmodified and silane‐modified forms of the mesoporous silica particles in the polymerization reaction increased the CMC of SDS. The presence of the unmodified mesoporous silica in the polymerization process led to instability in the batch emulsion polymerization process, as indicated by the formation of increased amounts of coagulum, and a decrease in the molecular weight of the polymer product. However, in comparison to the polymer formed in the absence of particle additives the molecular weight of the PMMA polymer increased with the amount of emulsifier and the addition of silane‐modified SBA‐15 particles, suggesting the growth of the polymer chains is facilitated at least in part by reaction in the pores of the particles. The improvement in molecular weight indicates that semi‐continuous MMA emulsion polymerization is best suited for the preparation of PMMA–mesoporous silica composites. POLYM. ENG. SCI., 54:2746–2752, 2014. © 2013 Society of Plastics Engineers     

Perfluorinated nanocomposite membranes modified by polyaniline: Electrotransport phenomena and morphology

This work summarizes results on the modification of perfluorinated sulfocationic membranes MF-4SC by in situ chemical polymerization of aniline. The investigation of transport properties of polyaniline/MF-4SC composite membranes after bulk modification - conductivity, diffusion and electroosmotic permeability, proton permselectivity - as well as porosimetry and polarization behavior is carried out as functions of aniline polymerization parameters and acid concentration. The fibrous-cluster model of a composite membrane is proposed for the estimation of transport and structural parameters, taking into account different mechanism of charge transfer in structural fragments of the composite. The atomic force microscopy images and curves of water distribution on the effective pore radii in the composite membranes testify to a morphological transition from the nano- to the microsize of polyaniline inclusions with increasing the aniline polymerization time. This effect is confirmed by the analysis of two-phase model transport and structural parameters. High values of the “true” proton transport numbers of composites are obtained and discussed. The dynamic hydration numbers of protons and chloride co-ions are estimated using the “true” transport numbers of protons and the electroosmotic coefficients of composites. The current-voltage curves of composite membranes in the “free standing” state after bulk and surface modification by polyaniline are investigated. The effect of stabilization of limiting current density is observed for MF-4SC membrane after bulk modification. The effect of current-voltage curves asymmetry is observed for different orientation of the polyaniline layer towards the current direction for an anisotropic composite membrane after surface modification.     

Direct synthesis of SILVER nanoparticles and polyaniline into the MESOPORES of SBA-15

The uniform structural pores architecture in nanoscopic domain of ordered mesoporous silicas, such as MCM-41 and SBA-15, can be used as a confined space to produce nanomaterials with controlled dimensions and cylindrical shape. In this study, we report the synthesis of a ternary nanocomposite constituted of silver nanoparticles and polyaniline concomitantly produced in the presence of SBA-15. The synthetic process involved firstly the adsorption of aniline vapor into the silica pores followed by its polymerization by reacting with the silver salt (AgN(SO₂CF₃)₂) solubilized in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (BMImTf₂N). With this synthetic approach the reaction proceeded quickly and efficiently, generating the silver-polyaniline nanocomposite mainly into pores and without collapsing the silica mesostructure. Surface area and pore volume of SBA-15 decreased after the reaction proceeded, indicating the formation of polyaniline and silver nanoparticles composite inside the pores and complementary analysis evidenced the presence of some silver nanoparticles outside pores. The measured electrical conductivity of the ternary composite in the order of 10^?6 S cm^?1 was coherent to the presence of the polymer and silver nanoparticles inside the pores of the insulator SBA-15 mesostructure rather than on the surface of the particles. The prepared SBA-15 ternary nanocomposite presented higher silver nanoparticles loadings of and superior surface area than the ones observed to small pore silicas, such MCM-41. The improvement in textural properties of the nanocomposite are favorable aspects for the further development of sensors and catalysts.

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Graphical abstract SBA-15 as a nanoreactor to produce AgNP-PANI nanocomposite, using an ionic liquid (BMImTf₂N) as solvent

     

PI/介孔氧化硅复合材料的制备与性能研究

通过四乙氧基硅烷的水解、缩合制备八(四甲基铵)倍半硅氧烷(TMA-POSS),以TMA-POSS为硅源,十六烷基三甲基溴化铵(CTAB)为模板荆,制备了六方有序纳米介孔氧化硅.采用原位聚合法制备了聚酰亚胺(PI)/介孔氧化硅复合材料,并讨论了介孔氧化硅的含量对PI材料的介电常数和热稳定性的影响.结果表明,加入介孔氧化硅有利于降低PI的介电常数和提高热稳定性,当其质量分数为5%时,PL/介孔氧化硅复合材料的介电常数可降至2.69.     

α-Amylase immobilization capacities of mesoporous silicas with different morphologies and surface properties

α-Amylase was encapsulated in several mesoporous materials (folded sheet mesoporous silica (FSM), cubic mesoporous silica (KIT-6), and two-dimensional hexagonal mesoporous silica (SBA-15)) that differed morphologically in terms of particle shape, pore size, and pore structure. The encapsulation capacity and thermal stability of encapsulated α-amylase were examined. The amount of α-amylase encapsulated increased with increasing pore size in the following order: SBA-15 < KIT-6 < FSM. Nitrogen adsorption experiments were performed before and after α-amylase encapsulation in mesoporous silicas with pore sizes larger than the size of α-amylase, confirming that α-amylase was encapsulated in the pores. Among mesoporous silicas with similar pore sizes, FSM was found to have the highest capacity for α-amylase encapsulation both per weight and per surface area of silica. Furthermore, α-amylase encapsulated in FSM demonstrated high thermal stability at 90 °C relative to the thermal stability of free α-amylase or free α-amylase encapsulated in other mesoporous silicas. Zeta potential measurements showed that the FSM surface had an isoelectric point that was lower than that of other mesoporous silicas, and hydrophilicity measurements showed that its surface was more hydrophilic. The surface properties of FSM contributed to the high thermal stability of the α-amylase encapsulated within the pores.     

Effect of the chemical characteristics of mesoporous silica MCM‐41 on morphological,thermal, and rheological properties of composites based on polystyrene

Mesoporous silica nanoparticles (MCM‐41) with an average diameter of ～ 20 nm were synthesized by a sol‐gel method using binary surfactant system. Polystyrene (PS) composites containing mesoporous silica nanoparticles were prepared by in situ polymerization of styrene monomers. Similar in situ polymerized PS composites were prepared based on the modified silica functionalized with methyl and vinyl groups. The effects of silylation on thermal and rheological properties of the PS/silica composites are investigated. Of particular importance is that the in situ polymerization of monomers within the mesoporous silica may trap some polymer chains, if not all, thereby affording a greater physical interaction between polymer and the porous fillers, whereas the chemical modification of silica surface promotes the polymer–filler interaction, which in turn enhances the thermal stability of composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of spherical mesoporous silica nanoparticles with nanometer-size controllable pores and outer diameters

Spherical mesoporous silica particles with tunable pore size and tunable outer particle diameter in the nanometer range were successfully prepared in a water/oil phase using organic templates method. This method involves the simultaneous hydrolytic condensation of tetraorthosilicate to form silica and polymerization of styrene into polystyrene. An amino acid catalyst, octane hydrophobic-supporting reaction component, and cetyltrimethylammonium bromide surfactant were used in the preparation process. The final step in the method involved removal of the organic components by calcinations, yielding the mesoporous silica particles. Interestingly, unlike common mesoporous materials, the particle with controllable pore size (4–15 nm) and particle diameter (20–80 nm) were produced using the method described herein. The ability to control pore size was drastically altered by the styrene concentration. The outer diameter was mostly controlled by varying the concentration of the hydrophobic molecules. Relatively large organic molecules (i.e. Rhodamine B) were well-absorbed in the prepared sample. Furthermore, the prepared mesoporous silica particles may be used efficiently in various applications, including electronic devices, sensors, pharmaceuticals, and environmentally sensitive pursuits, due to its excellent adsorption properties.     

Synthesis of Pt Nanowires Inside Aerosol Derived Spherical Mesoporous Silica Particles

Spherical mesoporous silica particles prepared by evaporation induced self assembly (EISA) were used as templates to form Pt nanowires. Transmission electron microscope (TEM) images of these aerosol-derived silica particles reveal hexagonally ordered pores coiled within each particle, with no obvious termination of the pores on the external surface. Near the particle surface the pores are seen to run parallel to the surface, consistent with the external constraint of spherical geometry. For MCM-41 type mesoporous materials, the pores are straight and accessible at either end for pore filling, but for spherical silica particles prepared by EISA, the pores are not open to the external surface. Hence it is remarkable that Pt nanowires can be formed within the closed pores inside these spherical silica particles, where conventional mechanisms of pore filling would not be expected to be operative. These results suggest that the silica walls in these mesoporous silica allow transport of volatile Pt complexes during wet reduction in H₂. The permeability to gases makes these spherical silica particles especially suitable for gas phase catalytic reactions, while at the same time confining metallic particles within the silica pores.     

Carbon black directed synthesis of ultrahigh mesoporous carbon aerogels

A simple modification of the conventional sol–gel polymerization of resorcinol–formaldehyde mixtures allowed a facile preparation of ultrahigh mesoporous carbon gels. In the conventional synthesis the growth of the cluster polymer particles leading to the development of the porosity is controlled by the R/C ratio. In the presence of a carbon conductive additive, the polymerization of the reactants proceeded through the formation of less-branched polymer clusters resulting in carbon gels with large pore volumes within the micro/mesoporous range. The obtained materials displayed unusual heterogeneous pore systems characterized by large mesopores interconnected by necks of variable sizes, along with an enhanced electrical conductivity provided by the carbon black additive. The gels showed stable electrochemical response in neutral aqueous electrolyte, being reversibly charged/discharged at large potential windows, without significant losses in the current density, chemical modifications or structural collapse. The enhanced life cycle of these electrodes makes them good candidates for their use in electrochemical applications where a fast response and high cycleability is required.     

合成条件对聚苯胺成纤性能的影响

以苯胺为单体、过硫酸铵为氧化剂、在盐酸水溶液中化学法合成聚苯胺 ,研究的重点是确立一个能够适合纺丝要求的合成参数体系。合成的聚苯胺重均相对分子质量达 2 9× 10 4。以不同条件下合成的聚苯胺为原料湿法纺制了聚苯胺导电纤维。     

Matrix synthesis of water-soluble polyaniline in the presence of polyelectrolytes

The matrix polymerization of aniline hydrochloride in the presence of polyanions with different chemical structures and molecular masses is studied. Poly(2-acrylamido-2-methyl-1-propanesulfonic acid) and poly(4-styrenesulfonic acid) or its sodium salt are used as polyelectrolyte matrices. It is shown that, if the polymerization of aniline hydrochloride is conducted in the presence of a polyelectrolyte matrix, water-soluble polyelectrolyte complexes in which polyaniline occurs in the form of an emeraldine salt are formed. The mechanism of polymerization is advanced. It is found that the sizes of polyaniline complexes in water are independent of the molecular mass of the polyelectrolyte matrix and its chemical structure.     

Simplifying the reaction system for the preparation of polyaniline nanofibers: Re-examination of template-free oxidative chemical polymerization of aniline in conventional low-pH acidic aqueous media

In this study, several polyaniline samples were prepared by oxidative chemical polymerization using only aniline, (NH₄)₂S₂O₈ and HCl in aqueous media at room temperature for morphological studies by SEM (scanning electron microscopy). The results show that polyaniline nanofibers can be obtained by template-free oxidative chemical polymerization in a conventional low-pH acidic aqueous medium (pH ～ 0) at room temperature. The study indicates that it is crucial to employ a mild post-polymerization processing procedure, such as dialysis, to preserve the as-formed morphology of polyaniline nanofibers. Our study also suggests that polyaniline could adopt the nanofiber structure as its intrinsic morphology when it is synthesized in a simple oxidative chemical polymerization system consisting of only aniline, (NH₄)₂S₂O₈ and HCl in an aqueous medium at room temperature.