Activation of the hydrolytic polymerization of ε-caprolactam by ester functions: Straightforward route to aliphatic polyesteramides

The hydrolytic polymerization of ε-caprolactam (CLa) was carried out in bulk (in absence of solvent) at 250 °C in the presence of carboxylic esters and aqueous H₃PO₂. It turned out that by conducting the ring opening polymerization (ROP) of CLa in the presence of PEO–C(O)–O–C₅H₁₁, a selected model ester (PEO = poly(ethylene oxide)), a remarkable activating effect of the ester function on the hydrolytic polymerization of the lactam was observed yielding PEO–b–PCLa diblock copolymers. The comparison of the CLa monomer conversions obtained with or without the model ester activated by H₃PO₂, as determined by ¹H NMR spectroscopy, has enabled to propose a multi-step mechanism in which three major reactions occurred: (i) ester and lactam hydrolysis, (ii) aminolysis of the carboxylic ester by the resulting primary amine of the hydrolyzed/opened lactam ring and (iii) condensation reactions between carboxylic acids and both amine/hydroxyl functions. The overall result of this multi-step mechanism can be assimilated as an “insertion” of the opened lactam into the ester function. By conducting the hydrolytic polymerization of CLa in the presence of an aliphatic polyester chain, such as poly(ε-caprolactone) (PCLo), polyesteramides were recovered with high yields and random distributions of the CLa and CLo repetitive units as determined by ¹³C NMR.     

Nanodispersed Au/Al2O3 catalysts for low-temperature CO oxidation: Results of research activity at the Boreskov Institute of Catalysis

This paper presents some important results of the studies on preparation and catalytic properties of nanodispersed Au/Al₂O₃ catalysts for low-temperature CO oxidation, which are carried out at the Boreskov Institute of Catalysis (BIC) starting from 2001. The catalysts with a gold loading of 1–2 wt.% were prepared via deposition of Au complexes onto different aluminas by means of various techniques (“deposition-precipitation” (DP), incipient wetness, “chemical liquid-phase grafting” (CLPG), chemical vapor deposition (CVD)). These catalysts have been characterized comparatively by a number of physical methods (XRD, TEM, diffuse reflectance UV/vis and XPS) and catalytically tested for combustion of CO impurity (1%) in wet air stream at near-ambient temperature. Using the hydroxide or chloride gold complexes capable of chemical interaction with the surface groups of alumina as the catalyst precursors (DP and incipient wetness techniques, respectively) produces the catalysts that contain metallic Au particles mainly of 2–4 nm in diameter, uniformly distributed between the external and internal surfaces of the support granules together with the surface “ionic” Au oxide species. Application of organogold precursors gives the supported Au catalysts of egg shell type which are either close by mean Au particle size to what we obtain by DP and incipient wetness techniques (CVD of (CH₃)₂Au(acac) vapor on highly dehydrated Al₂O₃ in a rotating reactor under static conditions) or contain Au crystallites of no less than 7 nm in size (CLPG method). Regardless of deposition technique, only the Cl-free Au/Al₂O₃ catalysts containing the small Au particles (d_i ≤ 5 nm) reveal the high catalytic activity toward CO oxidation under near-ambient conditions, the catalyst stability being provided by adding the water vapor into the reaction feed. The results of testing of the nanodispersed Au/Al₂O₃ catalysts under conditions which simulate in part removal of CO from ambient air or diesel exhaust are discussed in comparison with the data obtained for the commercial Pd and Pt catalysts under the same conditions.     

The dipeptide H-Aib-l-Ala-OH ligand in copper(II) chemistry: Variation of product identity as a function of pH

A systematic investigation of the influence of “pH” on the product identity from the Cu^II/H-Aib-l-Ala-OH (LH) reaction system is described, where H-Aib-l-Ala-OH is α-aminoisobutyryl-l-alanine. The pH variation has led to the synthesis of two discrete complexes, the structures of which have been determined by single-crystal X-ray crystallography. The “low pH” complex {[CuClL](H₂O)_2.5}_n (1) is a 3D coordination polymer, in which the dipeptide monoanion L⁻ behaves as a η¹:η¹:η¹:μ₂ ligand binding one Cu^II atom through its amino nitrogen and neutral peptide oxygen, and an adjacent Cu^II atom through one of its carboxylate oxygen. The “higher pH” complex {[Cu(H₋₁L)(EtOH)](EtOH)}_n (2) is a chain (1D) compound, in which the dipeptide dianion H₋₁L²⁻ uses its amino nitrogen, deprotonated peptide nitrogen and both carboxylate oxygens to bridge two metal centres.     

Nanostructured α- and β-cobalt hydroxide thin films

A new perspective in the use of electrochemical methods to deposit cobalt hydroxide thin films is presented. Ordered arrays of α-Co(OH)₂ (hydrotalcite-like (Co-HT)) and β-Co(OH)₂ nanoparticles were synthesized on transparent conductive oxide (TCO) substrates by localized cathodic electrogeneration of hydroxyl via the reduction of NO₂⁻ (or NO₃⁻) ion precursors in solution containing Co²⁺ in very low concentration. The thin films, analyzed by X-ray diffraction and scanning electron microscopy were found to be composed of vertically oriented platelets with the crystallographic c-axis parallel to the substrate surface. Turbostratic disorder was not observed in the films. UV/Vis spectra and thermal gravimetric analyses (TGA) indicated distinct variation between the Co-HT structures. Films deposited at 60 °C using a nitrite precursor generated uniform, vibrant-green mixed-valence Co-HT (Co²⁺/Co³⁺). Nitrate precursors yielded a “hydroxyl-deficient” Co-HT (Co²⁺ only). Films deposited at 95 °C in nitrate solution yielded β-Co(OH)₂. The films obtained in presence of nitrite were thicker than those obtained in nitrate. They were formed of β-Co(OH)₂ and contained traces of Co-HT.     

Preparation and characterization of novel main-chain azobenzene polymers via step-growth polymerization based on click chemistry

A novel α-azide and ω-alkyne A–B type azobenzene monomer, 3′-ethynylphenyl[4-(4-azidobutoxy)phenyl]azobenzene (EAPA), was synthesized and used to generate a novel polymer via step-growth polymerization using 1,3-dipolar cycloaddition reaction under the catalysis of CuSO₄·5H₂O/sodium ascorbate/H₂O (“Click” chemistry). The structure of the resultant main-chain azobenzene polymer, PEAPA, was characterized by GPC, ¹³C NMR, UV–vis and FT-IR spectra. Thermal stability and crystallinity of PEAPA powder were studied by TGA and WAXD. The photo-induced trans–cis isomerization of PEAPA and EAPA in N,N′-dimethyl formamide (DMF) solution was investigated. Furthermore, the thermal cis–trans isomerizations of PEAPA and EAPA were also observed at 60 °C in dark. Thermal stability and trans–cis–trans isomerization behavior of PEAPA was compared with its non-triazole analog, PDHA.     

N-PEG’ylation of chitosan via “click chemistry” reactions

N-azidated chitosan was prepared by four different methods: using azidated epichlorohydrin, sodium azide plius sodium nitrite, trifluoromethane sulfonyl azide or imidazole-1-sulfonyl azide hydrochloride. Using the two last reagents, the degree of azidation (DA) of chitosan was up to 40% and 65%, respectively. N-azidated chitosans with DA at about 60% were insoluble in aqueous and common organic solvents but dissolved in 5% LiCl solution in N-methyl-2-pyrrolidone, one of the very few solvents for chitin. Chitosan–methoxy poly(ethylene glycol) derivatives containing triazolyl moiety (chitosan-N-TMPEG comb copolymers) were prepared for the first time by coupling via 1,3-dipolar cycloaddition between pendant azide and end alkyne groups of chitosan and MPEG, respectively. Comb copolymers chitosan-N-TMPEG with degree of substitution (DS) of chitosan equal to DA of chitosan were synthesized at a certain excess of MPEG alkyne reaching DS up to 40%. “Clicking” of MPEG alkyne onto azidated chitosan was successful in binary mixture of water and methylene chloride but failed in 5% LiCl solution in N-methyl-2-pyrrolidone. Significant breakdown of chitosan backbone took place under “clicking” of MPEG in the presence of Cu(II)/ascorbate catalyst resulting in graft copolymers with bimodal MWD. Chitosan-N-TMPEG copolymers contained a certain residual amount of Cu and were soluble in acetate buffer (pH 3.7). Novel comb copolymers were characterized by FT-IR and ¹H NMR spectroscopy, SEC with triple detection, intrinsic viscosity, elemental and functional group analysis.     

Carbon nanotube-supported Pd–ZnO catalyst for hydrogenation of CO2 to methanol

A type of Pd–ZnO catalysts supported on multi-walled carbon nanotubes (MWCNTs) were developed, with excellent performance for CO₂ hydrogenation to methanol. Under reaction conditions of 3.0 MPa and 523 K, the observed turnover-frequency of CO₂ hydrogenation reached 1.15 × 10⁻² s⁻¹ over the 16%Pd_0.1Zn₁/CNTs(h-type). This value was 1.17 and 1.18 times that (0.98 × 10⁻² and 0.97 × 10⁻² s⁻¹) of the 35%Pd_0.1Zn₁/AC and 20%Pd_0.1Zn₁/γ-Al₂O₃ catalysts with the respective optimal Pd_0.1Zn₁-loading. Using the MWCNTs in place of AC or γ-Al₂O₃ as the catalyst support displayed little change in the apparent activation energy for the CO₂ hydrogenation, but led to an increase of surface concentration of the Pd⁰-species in the form of PdZn alloys, a kind of catalytically active Pd⁰-species closely associated with the methanol generation. On the other hand, the MWCNT-supported Pd–ZnO catalyst could reversibly adsorb a greater amount of hydrogen at temperatures ranging from room temperature to 623 K. This unique feature would help to generate a micro-environment with higher concentration of active H-adspecies at the surface of the functioning catalyst, thus increasing the rate of surface hydrogenation reactions. In comparison with the “Parallel-type (p-type)” MWCNTs, the “Herringbone-type (h-type)” MWCNTs possess more active surface (with more dangling bonds), and thus, higher capacity for adsorbing H₂, which make their promoting action more remarkable.     

Catalytic activity of supported metal particles for sulfuric acid decomposition reaction

Production of hydrogen by splitting of water in the thermochemical sulfur-based cycles that employs the catalytic decomposition of sulfuric acid into SO₂ and O₂ is of considerable interest. However, all of the known catalytic systems studied to date that consist of metal particles on oxide substrates deactivate with time on stream. To develop an understanding of the factors that are responsible for catalyst activity, we investigate the fresh activity of several platinum group metals (PGM) catalysts, including Pd, Pt, Rh, Ir, and Ru supported on titania at 850 °C and perform an extensive theoretical study (density-functional-theory-based first-principles calculations and computer simulations) of the activity of the PGM nanoparticles of different size and shape positioned on TiO₂ (rutile and anatase) and Al₂O₃ (γ- and η-alumina) surfaces. The activity and deactivation of the catalytic systems are defined by (i) the energy barrier for the detachment of O atoms from the SO_n (n = 1, 2, 3) species, and (ii) the removal rate of the products of the sulfuric acid decomposition (atomic O, S, and the SO_n species) from metal nanoparticles. We show that these two nanoscale features collectively result in the observed experimental behavior. The removal rate of the reaction products is always lower than the SO_n decomposition rates. The relation between these two rates explains why the “softer” PGM nanoparticles (Pd and Pt) exhibit the highest initial catalytic activity.     

Synthesis of onion-like mesoporous silica from sodium silicate in the presence of α,ω-diamine surfactant

Mesoporous silicas with vesicular and onion-like morphologies were assembled through hydrogen-bonding pathway from sodium silicate as silica source and electrically neutral α,ω-diamine, Jeffamine D2000 surfactant (H₂NCH(CH₃)CH₂[OCH₂CH(CH₃)]₃₃NH₂) as template in aqueous media at different synthesis temperatures (25, 60 and 100 °C). Assembling the material at 100 °C afforded onion-like core shell mesoporous silica, while at relatively lower temperature, e.g. 25 and 60 °C, multilamellar vesicles were obtained. Mesoporous silica with onion-like morphology was also obtained by a two-step synthesis involving an aging period of 20 h at room temperature followed by a hydrothermal stage (1–12 h) at 100 °C. The heavily cross-linked (Q⁴/Q³ ratio of 4.43) onion-like mesophase silica exhibited high hydrothermal stability. The BET surface area, pore volume and KJS (Kruk-Jaroniec-Sayari) pore diameter of the onion-like mesoporous silica were found to be 464 m² g⁻¹, 1.16 m³ g⁻¹ and 7.2 nm, respectively.     

Zeolite synthesised on copper foam for adsorption chillers: A mathematical model

In this work, a new adsorbent bed for adsorption chillers is proposed. Highly porous copper foams were directly sintered on the external surface of copper pipes. Afterwards, the foam surface was coated by several layers of zeolite 4A by in situ hydrothermal synthesis. The performance of an adsorbent bed based on the proposed configuration was then evaluated by a dynamic model. The results of simulations provided a cooling COP = 0.10–0.28, a specific cooling power ranging between 0.6 and 3.8 kW per kg of adsorbent material (77–123 W per kg of adsorber) and a volumetric cooling power of 103–214 kW per cubic meter of adsorber, depending on the copper foam thickness assumed (1–10 mm). A comparison with other “traditional” configurations based on loose pellets or consolidated layers of zeolite, demonstrated attractive performance – in terms of specific and volumetric powers – for the proposed adsorbent bed.     

Mesoscopic study of cylindrical phases of poly(styrene)-poly(isoprene) copolymer: Order–order phase transitions by temperature control

Phase transitions of cylindrical structures of poly(styrene)–poly(isoprene) copolymer (PS–PI) toward spherical and gyroid structures were explored using DPD simulations and a coarse-grained model. Cylindrical phases were first obtained within a composition interval (“predominance region”) 0.2 < f_PS < 0.26 (volume fraction of poly(styrene)). The predominance region of cylindrical structures was then subject to thermal heating cycles. The thermodynamic instabilities of cylindrical microdomains induce anisotropic composition fluctuations and phase transitions. A transition from the cylindrical phase at low composition limit to a spherical arrangement was observed during the thermal heating process. The cylindrical phase at the intermediate and high composition limit within the predominance region exhibits a transition towards a gyroid arrangement. The phase transition control during thermal heating on the cylindrical phases was governed by small variations in composition. The results are consistent with experimental studies.     

Thermal properties of the nitrogen-rich Ca-α-Sialons

Nitrogen-rich Ca-α-Sialon (Ca_xSi_12−2xAl_2xN₁₆ with x = 0.2, 0.4, and 0.8, 1.2 and 1.6) ceramics were prepared from the mixtures of Si₃N₄, AlN and CaH₂ powders in a hot press at 1800 °C using a pressure of 35 MPa and a holding time of 4 h, and then were investigated with respect to reaction mechanism, phase stability and oxidation resistance. In addition the sample with x = 1.6 was prepared in the temperature range 600–1800 °C using a pressure of 35 MPa and a holding time of 2 h. The α-Sialon phase was first observed at 1400 °C but the α-Si₃N₄ and AlN phases were still present at 1700 °C. Phase pure Ca-α-Sialon ceramics could not be obtained until the sintering temperature reached 1800 °C. The phase pure nitrogen-rich Ca-α-Sialon exhibited no phase transformation in the temperature range 1400–1600 °C. In general, mixed α/β-Sialon showed better oxidation resistance than pure α-Sialon in the low temperature range (1250–1325 °C), while α-Sialons with compositions located at α/β-Sialon border-line showed significant weight gains over the entire temperature range tested (1250–1400 °C). The phases formed upon oxidation were characterized by X-ray, SEM and TEM studies.     

Electrochemistry of thulium on inert electrodes and electrochemical formation of a Tm–Al alloy from molten chlorides

The electrochemical behaviour of TmCl₃ solutions was studied in the eutectic LiCl–KCl in the temperature range 673–823 K using inert and reactive electrodes, i.e. W and Al, respectively.On an inert electrode, Tm(III) ions are reduced to metallic thulium through two consecutive steps:

Tm(III) + 1e ↔ Tm(II) and Tm(II) + 2e ↔ Tm(0)

The electroreduction of Tm(III) to Tm(II) was found to be quasi-reversible. The intrinsic rate constant of charge transfer, k⁰, as well as of the charge transfer coefficient, α, have been calculated by simulation of the cyclic voltammograms and logarithmic analysis of the convoluted curves. Electrocrystallization of thulium plays an important role in the electrodeposition process, being the nucleation mode affected by temperature.The diffusion coefficients of Tm(III) and Tm(II) ions have been found to be equal. The validity of the Arrhenius law was verified by plotting the variation of the logarithm of the diffusion coefficients vs. 1/T.The electrode reactions of Tm(III) solutions at an Al electrode were also investigated. The results showed that for the extraction of thulium from molten chlorides, the use of a reactive electrode made of aluminium leading to Al–Tm alloys seems to be a pertinent route.Potentiometric titrations of Tm(III) solutions with oxide donors, using a ytria stabilized zirconia electrode “YSZE” as a pO²⁻ indicator electrode, have shown the formation of thulium oxychloride and thulium oxide and their corresponding solubility products have been determined at 723 K (pk_s(TmOCl) = 8.0 ± 0.3 pk_s(Tm₂O₃) = 18.8 ± 0.7).     

Precursor-mediated dissociation of n-butane on a PdO(1 0 1) thin film

We investigated the molecular adsorption and dissociation of n-butane on a PdO(1 0 1) thin film using temperature-programmed reaction spectroscopy (TPRS) experiments and density functional theory (DFT) calculations. At low coverage, n-butane adsorbs on PdO(1 0 1) in a molecular state that is more strongly bound than n-butane physisorbed on Pd(1 1 1). This molecularly adsorbed state of n-butane on PdO(1 0 1) corresponds to a σ-complex that forms on the rows of coordinatively unsaturated (cus) Pd atoms of the oxide surface. TPRS results show that a fraction of the n-butane layer undergoes C–H bond cleavage below 215 K and that the resulting fragments are completely oxidized by the surface upon continued heating. The evolution of product yields with the n-butane coverage as well as site blocking experiments provide strong evidence that the n-butane σ-complex serves as the precursor to initial C–H bond cleavage of n-butane on PdO(1 0 1). DFT calculations confirm the formation of an n-butane σ-complex on PdO(1 0 1). In the preferred bonding geometry, the n-butane molecule aligns parallel to a cus-Pd row and adopts a so-called η¹(2H) configuration with two coordinate H–Pd bonds per molecule. Our DFT calculations also show that σ-complex formation weakens C–H bonds, causing bond elongation and vibrational mode softening. For methane, we predict that coordination with a cus-Pd atom lowers the barrier for C–H bond cleavage on PdO(1 0 1) by more than 100 kJ/mol. These results demonstrate that dative bonding between alkane molecules and cus-Pd atoms serves to electronically activate C–H bonds on PdO(1 0 1) and suggest that adsorbed σ-complexes play a general role as precursors in alkane activation on transition metal oxide surfaces.     

Adsorption properties of composite materials (LiCl + LiBr)/silica

This paper presents experimental data on synthesis and the phase composition of novel composites “(LiCl + LiBr) confined to the silica gel pores” as well as their sorption equilibrium with water and methanol vapour. Phase transformation of the composites during methanol sorption was characterized in situ by an X-ray diffraction analysis. The isobars of sorption on the composites were measured in the temperature range T = 303–383 K at the methanol and water pressure P = 107 and 13 mbar, respectively, using a thermo-gravimetric technique. It was shown that the formation of solid solutions of LiCl and LiBr took place in limited ranges of LiBr (C_Br = 0–11 mol.%) and LiCl (C_Cl = 0–36 mol.%) content. These solutions absorbed water (methanol) at temperature that was intermediate between the individual solvation temperatures for confined LiCl and LiBr. In the composites with LiCl/LiBr molar ratio between the ranges of solubility a mixture of two solid solutions was formed. Each solution absorbed water (methanol) independently at a certain temperature. The use of the binary LiCl–LiBr system confined to the silica pores can be an effective tool for designing innovative materials with predetermined sorption properties.     

An α-K3PMo3W9O40 film loaded with silver nanoparticles: Fabrication, characterization and properties

A composite film consisting of the mixed-addenda Keggin-type polyoxometalate α-K₃PMo₃W₉O₄₀ (PMo₃W₉) and silver nanoparticles (AgNPs) was fabricated on quartz, silicon, and ITO by the layer-by-layer self-assembly method. The regular growth of the multilayer film was monitored by UV–vis spectroscopy, and the morphology was measured by atomic force microscopy (AFM). The multilayer film embedded by AgNPs exhibited the photo-luminescence ascribed to electronic transitions from excited states to d levels of the silver nanoparticles. The composite film also showed electrocatalytic activity towards reduction of NO₂⁻, H₂O₂, ClO₃⁻, BrO₃⁻, and IO₃⁻ attributed to tungsten-centered and molybdenum-centered redox processes of PMo₃W₉.     

Effect of ethyleneglycol addition on the properties of P-doped NiMo/Al2O3 HDS catalysts: Part I. Materials preparation and characterization

Phosphorous-doped NiMo/Al₂O₃ hydrodesulfurization (HDS) catalysts (nominal Mo, Ni and P loadings of 12, 3, and 1.6 wt%, respectively) were prepared using ethyleneglycol (EG) as additive. The organic agent was diluted in aqueous impregnating solutions obtained by MoO₃ digestion in presence of H₃PO₄, followed by 2NiCO₃·3Ni(OH)₂·4H₂O addition. EG/Ni molar ratio was varied (1, 2.5 and 7) to determine the influence of this parameter on the surface and structural properties of synthesized materials. As determined by temperature-programmed reduction, ethyleneglycol addition during impregnation resulted in decreased interaction between deposited phases (Mo and Ni) and the alumina carrier. Dispersion and sulfidability (as observed by X-ray photoelectron microscopy) of molybdenum and nickel showed opposite trends when incremental amounts of the organic were added during catalysts preparation. Meanwhile Mo sulfidation was progressively decreased by augmenting EG concentration in the impregnating solution, more dispersed sulfidic nickel was evidenced in materials synthesized at higher EG/Ni ratios. Also, enhanced formation of the so-called “NiMoS phase” was registered by increasing the amount of added ethyleneglycol during simultaneous Ni–Mo–P–EG deposition over the alumina carrier. That fact was reflected in enhanced activity in liquid-phase dibenzothiophene HDS (batch reactor, T = 320 °C, P = 70 kg/cm²) and straight-run gas oil desulfurization (steady-state flow reactor), the latter test carried out at conditions similar to those used in industrial hydrotreaters for the production of ultra-low sulfur diesel (T = 350 °C, P = 70 kg/cm², LHSV = 1.5 h⁻¹ and H₂/oil = 2500 ft³/bbl).     

Non-thermal plasma-assisted catalytic NOx storage over Pt/Ba/Al2O3 at low temperatures

NO_x storage performances have been investigated on a Pt/Ba/Al₂O₃ catalyst by comparison using two types of non-thermal plasma (NTP) reactor: the “PDC system” reactor and the “PFC system” reactor. In the PDC system, the catalyst was placed in the discharge space and was activated by the plasma directly, whereas in the PFC system, the plasma reactor was followed by the catalyst. The results showed that the NO_x storage capacity (NSC) of the Pt/Ba/Al₂O₃ catalyst was significantly enhanced by the non-thermal plasma in the PDC and PFC system, and the PDC system exhibited better promotional effect than the PFC system in the temperature range of 100–300 °C. The NSC of the catalyst was increased with the increase of the input energy density both in the PDC and PFC system due to the higher NO oxidation at higher input energy density. It was also found that the ionic wind induced by plasma in the PDC system enhanced the quantity of the NO adsorbed onto the catalyst surface and therefore could react with the O-radical to form more NO₂, and thus promote the formation of nitrate on the catalyst.     

Nanoparticles of iron and vanadium oxides supported on iron substituted LDHs: Synthesis, textural characterization and their catalytic behavior in ethylbenzene dehydrogenation

Nanostructured catalysts derived from nanoparticles of iron or vanadium oxides supported on the matrices of iron substituted hydrotalcite-like anionic clays (layered double hydroxides, LDHs) have been obtained and tested in the process of ethylbenzene dehydrogenation to styrene. A simple synthesis method based on the LDHs “memory effect” has been used to prepare the new oxides-anionic clay structures. TEM analysis shows that on the typical FeLDH particles (average size equal to 75 nm) smaller nanoparticles are supported; their average size is equal to 7 and 11 nm for Fe/FeLDH and V/FeLDH respectively. XPS analysis indicates the presence of Fe₂O₃ and V₂O₃ on the surface of the supported LDHs. N₂ adsorption at 77 K reveals that the supported anionic clays have less accentuated mesoporous properties in comparison to the parent FeLDH matrix. The catalytic behavior of the samples is a function of the nature of the supported nanoparticles.     

Preparation of conducting polyaniline/TiO2 composite submicron-rods by the γ-radiolysis oxidative polymerization method

Conducting polyaniline (PAni)–titanium dioxide (TiO₂) composite micron-sized rods have been synthesized using an in situ gamma radiation-induced chemical polymerization method. Aqueous mixtures of aniline, a free-radical oxidant and/or titania nanoparticles were irradiated with γ-rays. The formation of PAni–TiO₂ composite submicron-rods is the result of free aniline cation-radicals and adsorbed aniline cation-radicals on the surface of TiO₂ nanoparticles growing together with the aid of high-energy gamma irradiation. SEM and TEM images represent the PAni–TiO₂ composite rods as having a diameter range of 0.2–0.5 μm. Electrical conductivities were checked by the standard four-point probes method and found to be 0.28 S/cm for bulk PAni and 0.15 S/cm for PAni–TiO₂ composite submicron-rods. UV–visible absorption spectroscopy showed two electronic bands at about 320 and 596 nm for bulk PAni and blue-shifted bands due to the formation of PAni–TiO₂ composites. Thermogravimetric analysis revealed that the composites have a higher degradation temperature than polyaniline alone.