Preparation and characterization of polyaniline/manganese dioxide composites and their catalytic activity

This paper is devoted to the preparation of polyaniline/MnO2 (PANI/MnO2) composites via chemical oxidation of aniline in H2SO4 medium using beta-MnO2 as an oxidant. The parameters affecting the polymerization reaction are considered. These parameters are [aniline], amount of beta-MnO2, stirring time, and polymerization temperature. SEM, FT-IR, XRD, and TGA techniques are used to characterize the resulting composites. XRD measurements reveal the distortion of the crystal structure of beta-MnO2 after the polymerization reaction. Thus, the XRD pattern of PANI is predominating. The crystalline composites are obtained using higher molar ratio of [Ox]/[ANI] and at higher temperature. Increasing the amount of beta-MnO2 led to an increase in the acidic character of the obtained composites due to adsorption of excess H+ on the oxide surface. The thermal stability of the composites decreased with increasing both [aniline] and stirring time, while it increased with increasing amount of beta-MnO2. The applications of the composites in the oxidative degradation of Direct Red 81, Acid Blue 92, and Indigo Carmine dyes exhibited good catalytic activity in the presence of H2O2 as an oxidant. The reactions followed first-order kinetics and the rate constants were determined. The degradation reaction involved the catalytic action of the PANI counterpart of the composite toward H2O2 decomposition, which can lead to the generation of HO radicals as a highly efficient oxidant attacking the target dyes. The detailed kinetic studies and the mechanism of these catalytic reactions are under consideration in our group.     

Synthesis and characterization of polyaniline/silicon dioxide composites and preparation of conductive films

The focus of this study was to synthesize the inherently conductive polymer polyaniline using an optimized process to prepare polyaniline/silicon dioxide (PANI/SiO₂) composites by in situ polymerization and ex situ solution mixing. PANI and PANI/SiO₂ composite films were prepared by drop‐by‐drop and spin coating methods. The electrical conductivities of HCl doped PANI film and PANI/SiO₂ composite films were measured according to the standard four‐point‐probe technique. The composite films exhibited an increase in electrical conductivity over neat PANI. PANI and PANI/SiO₂ composites were also investigated by spectroscopic methods including UV‐Vis, FT‐IR, and Photoluminescence. UV‐Vis and FT‐IR studies showed that SiO₂ particles affect the quinoid units along the polymer backbone and indicate strong interactions between the SiO₂ particles and the quinoidal sites of PANI (doping effect). The photoluminescence properties of PANI and PANI/SiO₂ composites were studied and the PANI/SiO₂ composites showed increased intensity as compared to neat PANI. The increase of conductivity of PANI/SiO₂ composite may be partially due to the doping or impurity effect of SiO₂ where the silicon dioxides compete with chloride ions. The morphology of particles and films were examined by a scanning electron microscope (SEM). SEM measurements indicated that the SiO₂ were well dispersed and isolated in composite films. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation and characterization of composite polyaniline materials for catalytic purposes

Composite film electrodes were prepared by open-circuit Pt deposition on polymeric PANI films that were electrosynthesized from aniline acid solutions with suspended carbon particles (CPs). Gold, nickel, and a Ni-based alloy, Nichrome, were used as substrates, and carbon particles, carbon nanotubes (CNT), and Vulcan XC-72R carbon black, suspended in the monomer acid solution, were incorporated into the film. Pt particles were dispersed on films grown on Ni-based substrates by deposition from a Pt(IV) acid solution at open circuit (OC). CNT trapped into the PANI films have a favorable influence on Pt dispersion. The novel composite electrodes showed significant catalytic activity for methanol oxidation.     

An effective nanocomposite of polyaniline and ZnO: preparation,characterizations, and its photocatalytic activity

The polyaniline/zinc oxide (PANI/ZnO) nanocomposites were prepared by in situ polymerization of aniline monomer with ZnO nanomaterials and applied as a photocatalyst for the degradation of methylene blue (MB) dye. The morphological observations elicited the agglomerations of PANI sheets which occurred due to the interaction between PANI and ZnO nanomaterials in PANI/ZnO nanocomposites. As compared to pristine PANI, the UV–vis spectra exhibited that the absorption peak of π–π* transitions considerably shifted to higher wavelength at 360 nm from 325 nm in the nanocomposites. The photocatalytic activity results indicated the substantial degradation of MB dye by ~76% over the surface of PANI/ZnO nanocomposite catalyst under light illumination. The PANI/ZnO nanocomposites showed three times higher photocatalytic activity to MB dye degradation compared to pristine PANI might due to high photogenerated electron (ē)–hole (h⁺) pairs charge separation.     

Gold nanowire networks: synthesis, characterization, and catalytic activity

Gold nanowire networks (AuNWNs) with average widths of 17.74 nm (AuNWN(1)) or 23.54 nm (AuNWN(2)) were synthesized by direct reduction of HAuCl(4) with sodium borohydride powder in deep eutectic solvents, such as ethaline or reline, at 40 °C. Their width and length were dependent on the type of solvent and the NaBH(4)/HAuCl(4) molar ratio (32 in ethaline and 5.2 in reline). High resolution transmission electron microscopy (HR-TEM) analysis of the gold nanowire networks showed clear lattice fringes of polycrystalline nanopowder of d = 2.36, 2.04, 1.44, and 1.23 ? corresponding to the (111), (200), (220), or (311) crystallographic planes of face centered cubic gold. The purified AuNWNs were used as catalysts for the chemical reduction of p-nitroaniline to diaminophenylene with sodium borohydride in aqueous solution. The reaction was monitored in real time by UV-vis spectroscopy. The results show that the reduction process is six times faster in the presence of gold nanowire networks stabilized by urea from the reline (AuNWN(2)) than in the presence of gold nanowire networks stabilized by ethylene glycol from ethaline (AuNWN(1)). This is due to a higher number of corners and edges on the gold nanowires synthesized in reline than on those synthesized in ethaline as proven by X-ray diffraction (XRD) patterns recorded for both types of gold nanowire networks. Nevertheless, both types of nanomaterials determined short times of reaction and high conversion of p-nitroaniline to diaminophenylene. These gold nanomaterials represent a new addition to a new generation of catalysts: gold based catalysts.     

Preparation, characterization, and photocatalytic activity of polyaniline/ZnO nanocomposite

Polyaniline (PANI)/zinc oxide (ZnO) nanocomposite was synthesized by in-situ polymerization. X-ray diffraction patterns, UV?Cvisible spectroscopy, SEM, and TEM were used to characterize the composition and structure of the nanocomposite. Nanostructured PANI/ZnO composite was used as photocatalyst in the photodegradation of methylene blue dye molecules in aqueous solution. The photocatalytic activity of PANI/ZnO nanocomposite under UV and visible light irradiation was evaluated and was compared with that of ZnO nanoparticles. ZnO/PANI core?Cshell nanocomposite had greater photocatalytic activity than ZnO nanoparticles and pristine PANI under visible light irradiation. According to these results, application of PANI as a shell on the surface of ZnO nanoparticles causes the enhanced photocatalytic activity of the PANI/ZnO nanocomposite. Also UV?Cvisible spectroscopy studies showed that the absorption peak for PANI/ZnO nanocomposite has a red shift toward visible wavelengths compared with the ZnO nanoparticles and pristine PANI. The effect of different operating conditions on the photocatalytic performance of PANI/ZnO nanocomposite in the photodegradation of methylene blue dye molecules was investigated in a bath experimental setup.     

Iron-oxide-modified nanosized diamond: preparation, characterization, and catalytic properties in methanol decomposition

Nanosized diamond (UDD), obtained by a detonation procedure, was modified with iron from the corresponding acetylacetonate precursor under various pretreatment conditions. Nitrogen physisorption, X-ray diffraction, temperature-programmed reduction, and FTIR and M?ssbauer spectroscopy were used for their characterization. The samples' catalytic behavior in methanol decomposition was also studied. The physicochemical and catalytic properties of the obtained materials (Fe/UDD) were compared with those of other iron-oxide-modified mesoporous supports with different nature and functionality (MCM-48 silica and CMK-1 carbon). The highest catalytic activity and stability was achieved with air-pretreated Fe/UDD.     

Synthesis and characterization of polyaniline: nanospheres,nanorods, and nanotubes—catalytic application for sulfoxidation reactions

The synthesis of nanostructured polyaniline (PANI) with different morphologies by simple alkali‐guided template‐free method followed by doping them with vanadium has been described. The synthesized polyaniline nanoparticles have been well characterized by various techniques. Further, the catalytic activity of the undoped and doped PANI nanostructures for selective oxidation of sulfides to sulfoxides in water has been studied. It was observed that the special morphology of nanostructures plays an important role in enhancement of catalytic activity. Vanadium‐doped PANI nanotubes and nanorods showed higher activity and selectivity than nanospheres. The catalyst has been reused for five consecutive cycles with consistent activity. Copyright © 2008 John Wiley & Sons, Ltd.     

Spinel copper ferrite nanoparticles: Preparation,characterization and catalytic activity

The magnetic CuFe₂O₄ nanoparticles have been synthesized and characterized by various spectroscopic methods, including X‐ray diffraction (XRD), O K, Cu and Fe K ‐edge X‐ray absorption near edge structure (XANES), energy dispersive X‐ray analysis (EDX), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The azide‐alkyne cycloaddition by the reaction of various phenylacetylenes with a mixture of benzyl halides and NaN₃ and also three component (A³) coupling reaction of aldehyde, alkyne and amine catalyzed by CuFe₂O₄ nanoparticles under aerobic conditions led to the formation of the 1,4‐disubstituted‐1,2,3‐triazoles and propargylamines in excellent yields. The catalyst can be recovered by applying an external magnetic field for the subsequent cycloaddition reactions and reused without any tangible loss in catalytic efficiency.     

Formation,characterization and catalytic activity of PD-polyheteroarylenes complexes

High molecular weight polybenzimidazoles, poly[(N-phenyl)benzimidazoles], polynaphthoylenebenzimidazoles and poly(naphthoylene-s-triazoles) were obtained using well-known polycyclodehydration processes as well as new reactions for their preparation -reductive polyheterocyclization and “activated” poly-cyclocondensation. Treatment of polymers obtained with PdCl₂ led to the formation of Pd-containing polyheteroarylenes complexes. Pd^II bound to the polymers was reduced to Pd° by treatment with hydrogen or NaBH₄. Pd-polyheteroarylenes complexes obtained may be used as catalysts for the hydrogenation of alkenes and alkynes, for the selective hydrogenation of the triple bonds of unsaturated hydrocarbons in the presence of double bonds etc. Of especially great interest is the utilization of Pd-polybenzimidazole as catalyst for carbonylation of nitrobenzene and different halogen-substitited nitrobenzenes in the presence of alcohols leading to the formation of carbamates.     

Tungstate sulfuric acid: preparation, characterization, and application in catalytic synthesis of novel benzimidazoles

Tungstate sulfuric acid (TSA) was prepared, characterized, and applied for direct synthesis of novel and known benzimidazoles through a condensation reaction of o-phenylenediamines with orthoesters under solvent-free conditions. TSA was characterized by powdered X-ray diffraction (XRD), X-ray fluorescence (XRF), and FTIR spectroscopy. This novel and eco-friendly method is very cheap and has many advantages such as excellent yields, recyclable and eco-friendly catalyst, and simple work-up procedure.     

Dinickel(II) complexes: preparation and catalytic activity

Ligands (L(a-c)) based on 2,7-bis(3,5-di-R-pyrazol-1-yl)-1,8-naphthyridine (a, R = H; b, R = CH(3); c, R = Ph) were prepared for the construction of a series of dinickel complexes. Treatment of L(x) with NiCl(2) in an anhydrous methanol/THF solution resulted in the formation of dinuclear complexes [(L(x))(μ-Cl)(2)Ni(2)Cl(2)(CH(3)OH)(2)] (3, x = a; 4, x = b; 5, x = c). These new complexes were characterized by elemental analysis, IR and UV-Vis spectroscopic techniques. The structures of complexes 3 and 4 were further confirmed by X-ray diffraction studies. Interestingly, crystals of 4 were obtained as a co-crystallization of 4 and the methanol substituted species [{(L(b))(μ-Cl)(2)Ni(2)Cl(CH(3)OH)(3)}Cl] (4'). These dinickel complexes have been tested in the catalytic homo-coupling of terminal alkynes with the use O(2) as the oxidant, showing excellent activities. A clear improvement on the catalytic activity of these complexes is observed as compared to the mono-nuclear species.     

Syntheses,characterization and catalytic activity of peroxo tantalum polyoxotungstates

Peroxo-tantalum and tantalum mono-substituted tungstosilicates with the Keggin structure, K₅[-SiW₁₁Ta(O₂) O₃₉]18H₂O (1) and K₅[-SiW₁₁TaO₄₀]14H₂O (2) respectively, and peroxo-tantalum and tantalum mono-substituted tungstophosphates with the Wells–Dawson structure K₇[₂-P₂W₁₇Ta(O₂)O₆₁]16H₂O (3) and K₇[₂-P₂W₁₇TaO₆₂]14H₂O (4), respectively, were prepared by stereoselective synthesis and characterized by elemental analysis, i.r. and u.v. spectroscopy, XPS, ³¹P and ¹⁸³W n.m.r. spectroscopy, and polarography, as well as cyclic voltammetry. The presence of a peroxo group in the complexes (1) and (3) was supported by observation of an i.r. band due to the —O—O— bond at 881 cm^–1, the charge transfer bands of (²—O₂)Ta at ca. 316 and 389 nm, the O_1s binding energy at 532.0 eV and a new irreversible reduction polarographic wave at E_1/2 0.1 V, assigned to the reduction of peroxo group and which enhances the oxidant properties of the heteropoly anions. There are six lines for complex (1) and nine lines for complex (3) in the ¹⁸³W n.m.r. spectra, showing that the complex (1) has a mono-substituted Keggin structure and complex (3) has a mono-substituted ₂-Wells–Dawson structure. The catalytic activities of the complexes with respect to epoxidation of maleic acid with H₂O₂ as oxidant were examined and the best result, 83.5% yield, was obtained for [(C₄H₉)₄N]₅[-SiW₁₁Ta(O)₂O₃₉]·18H₂O.     

Mandelate and prolinate ionic liquids: synthesis, characterization, catalytic and biological activity

A group of quaternary ammonium mandelates and l-prolinates, as ionic liquids, were synthesized and characterized. The prepared salts were soluble in water and showed high surface activity. The described synthesis of l-prolinate was simple and the obtained ionic liquid contained a chiral anion. l-Prolinate in CH₂Cl₂ was employed for the asymmetric Michael addition of a ketone to nitrostyrene. A yield of 60%, enantioselectivity (upto 50% ee), and good diastereoselectivity (syn/anti ratio of up to 90:10) were obtained for the asymmetric addition of cyclohexanone. These novel ionic liquids proved to be very effective anti-microbial and anti-fungal agents, especially didecyldimethylammonium l-prolinate. Additionally, it was found that phytotoxicity can be a useful tool in assessing the optical forms of ionic liquids.     

Preparation,characterization and catalytic activity of biomaterial-supported copper nanoparticles

Synthesis of copper nanoparticles was carried out with nanocrystalline cellulose (NCC) as a support by reducing CuSO₄·5H₂O ions using hydrazine. Ascorbic acid and aqueous NaOH were also used as an antioxidant and pH controller, respectively. The synthesized copper nanoparticles supported on NCC (CuNPs@NCC) were characterized by UV–vis, XRD, TEM, XRF, TGA, DSC, N₂ adsorption-desorption method at 77 K and FTIR. The UV–vis confirmed the formation and stability of the CuNPs, which indicated that the maximum absorbance of CuNPs@NCC was at 590 nm due to the surface plasmon absorption of CuNPs. Morphological characterization clearly showed the formation of a spherical structure of the CuNPs with the mean diameter and standard deviation of 2.71 ± 1.12 nm. Similarly, XRD showed that the synthesized CuNPs@NCC was of high purity. The thermal analysis showed that the CuNPs@NCC exhibited better thermal behaviors than NCC. BET surface area revealed that the N₂ adsorption–desorption isotherms of CuNPs@NCC featured a type IV isotherm with an H3 hysterisis loop. This chemical method is simple, cost effective, and environmentally friendly. Compared to NCC-supported CuNPs and unsupported CuNPs, the as-prepared CuNPs@NCC exhibit a superior catalytic activity and high sustainability for the reduction of methylene blue with NaBH₄ in aqueous solution at room temperature. The CuNPs@NCC achieved complete reduction of MB with completion time, rate constant and correlation coefficient (R ²) of 12 min, 0.7421 min^?1 and 0.9922, respectively.     

聚苯胺复合二氧化钛的制备及其降解硝基苯研究

以苯胺和二氧化钛为原料,采用化学氧化法,合成光降解复合材料聚苯胺(PANI)/二氧化钛(TiO2),并对其进行表征.采用该复合材料对50mg·L-1的硝基苯模拟废水进行自然光催化降解研究,实验结果显示,当二氧化钛和苯胺用量摩尔数之比为10:1,在自然光条件下获得最佳的催化效果,同时讨论了不同pH值和投加量对降解效果的影...     

Preparation and characterization of polyaniline/manganese dioxide composites via oxidative polymerization: Effect of acids

Polyaniline/manganese dioxide (PANI/MnO₂) composites have been chemically prepared by oxidative polymerization of aniline in acidic medium containing MnO₂ as an oxidant. The acids used were; H₂SO₄, HNO₃, HCl, and H₃PO₄ The prepared composites were characterized by SEM, elemental analysis, FT-IR, XRD, TGA, and magnetic susceptibility. XRD measurements of the composites revealed that the crystal structure of incorporated MnO₂ undergone a distortion and converted into amorphous. Thus, the XRD pattern of PANI was predominate. The degree of crystallinity of the prepared composites is depended on the type of compensated acid anions and has the order; . This order is agrees with the order of crystallographic radii and the shape of the corresponding acid anions. From the value of point zero charge of MnO₂ (pzc at pH ≈7.5) and FT-IR spectra, it was concluded that adsorbed acids anions on the oxide surface works as the charge compensator for positively charge PANI in the formation of PANI/MnO₂. The content of PANI in the composite was depended on the type of acid used. Thermogravimetric study exhibited that the composite with low content of PANI has a higher thermal stability. Magnetic susceptibility measurements revealed that the composites has a diamagnetic properties. A schematic composition of the composites has been suggested.     

CdS nanoparticles deposited on montmorillonite: preparation, characterization and application for photoreduction of carbon dioxide

CdS nanoparticles were precipitated by the reaction of cadmium acetate with sodium sulphide in the presence of cetyltrimethylammonium (CTA) and deposited on montmorillonite (MMT). The resulting CdS-MMT nanocomposite contained 6 wt.% of CdS and 30 wt.% of CTA. Band-gap energy of CdS was estimated at 2.63±0.09 eV using the Tauc plot. The size of CdS nanoparticles was calculated from the band-gap energy at 5 nm and from the micrographs of transmission electron microscopy (TEM) at 5 nm. Selected area electron diffraction (SAED) recognized the cubic structure of CdS (Hawleite). The dynamic light scattering (DLS) method confirmed that CdS nanoparticles were anchored on the surface of MMT particles. CTA was found to be intercalated into MMT and adsorbed on its external surface. CdS-MMT was used for the photoreduction of carbon dioxide dissolved in NaOH solutions. The yields of originating gas products can be arranged in the order: H(2) ? CH(4) > CO. Amounts of these products were 4-8 folds higher then those obtained with TiO(2) Evonic P25. Hydrogen reduced CO(2) to CO and CH(4).     

Cu-incorporated mesoporous materials: Synthesis, characterization and catalytic activity in phenol hydroxylation

A series of novel Cu-incorporated mesoporous materials (CMMs) with molar ratios of Cu/Si ranging from 1/200 to 1/20 were synthesized by sol–gel method using glutaric acid as template. The materials were characterized by powder X-ray diffraction (XRD), N₂ adsorption, diffuse reflectance UV–vis spectroscopy and transmission electron microscopy (TEM). The results indicate that the CMMs have a three-dimensional (3D) worm-like mesoporous structure with a surface area between 600 and 800 m² g⁻¹ and the copper ions are incorporated into the matrix with octahedral environment. The catalytic activity of these CMMs in the phenol hydroxylation using H₂O₂ as oxidant is comparable to that of TS-1. Effects of Cu/Si molar ratio in the catalyst and the influence of various reaction parameters on the catalytic activity were investigated in detail and the optimized reaction condition was acquired.