Low-temperature fabrication of TiO<Subscript>2</Subscript> film on flexible substrate by atmospheric roll-to-roll CVD

Titanium dioxide (TiO₂) thin film was fabricated using titanium isopropoxide as a precursor through an atmospheric low-temperature roll-to-roll chemical vapor deposition method. TiO₂ was deposited on the PET substrate in the temperature range of room temperature to 100°C, and the working pressure was 740 Torr. The surface morphology of TiO₂ thin film was analyzed by field emission scanning electron microscopy and a 2D surface profiler. The results revealed that the growth rate of TiO₂ film was 31 nm/min at 100°C, and it also showed that the surface is uniform and smooth. Moreover, the lowest root mean square roughness (R _q) value of 1.87 nm was obtained for TiO₂ film prepared at 100°C. The composition of TiO₂ film was confirmed by X-ray photoelectron spectroscopy (XPS) analysis. The film showed very good chemical and optical properties while increasing the substrate deposition temperature. The UV–Vis spectroscopy analysis revealed that TiO₂ films exhibited excellent optical transmittance, more than 91% observed in the visible region.     

Mg(OH)<Subscript>2</Subscript> Films Prepared by Ink-Jet Printing and Their Photocatalytic Activity in CO<Subscript>2</Subscript> Reduction and H<Subscript>2</Subscript>O Conversion

Mg(OH)₂ films on Al substrates were fabricated by ink-jet printing, and they were applied as photocatalysts in solar fuels production (H₂ and CH₃OH) from CO₂ and H₂O conversion. The films were fabricated by means of a deposition of a solution composed of magnesium complex nanoparticles over aluminum foils, which were submitted to a heat treatment to promote the crystallization of Mg(OH)₂. The films were characterized by razing incidence X-ray diffraction (GZXD), Fourier-transform infrared spectroscopy (FTIR), Scanning electronic microscopy, X-ray photoelectron spectroscopy (XPS), and N₂ physisorption by BET method. The Mg(OH)₂ was detected in all the samples synthesized with 1 to 40 layers. According to XPS and FTIR analysis, it was detected the presence of carbonates related to Mg₃O(CO₃)₂ and Al⁰ and Al³⁺ due to the substrate. The highest photocatalytic activity was reached using 30 layers of Mg(OH)₂ for H₂ and CH₃OH generation, which it was 268 and 15 µmol g^??1h^??1, respectively. These results were associated to the presence of adequate amounts of MgO and Al₂O₃ that promote an efficient transfer of the photogenerated electrons between them. Furthermore, the formation of porous structures with high surface area and relative high roughness promoted an increase in the mass transport between the gas and liquid phase, which increase the effectiveness of the photocatalysts.     

Preparation of hydrophobic SiO<Subscript>2</Subscript>@(TiO<Subscript>2</Subscript>/MoS<Subscript>2</Subscript>) composite film and its self-cleaning properties

TiO₂/MoS₂ composite was encapsulated by hydrophobic SiO₂ nanoparticles using a sol–gel hydrothermal method with methyltriethoxysilane (MTES), titanium tetrachloride (TiCl₄), and molybdenum disulfide (MoS₂) as raw materials. Then, a novel dual functional composite film with hydrophobicity and photocatalytic activity was fabricated on a glass substrates via the combination of polydimethylsiloxane adhesives and hydrophobic SiO₂@(TiO₂/MoS₂) composite particles. The influence of the mole ratios of MTES to TiO₂/MoS₂ (M:T) on the wettability and photocatalytic activity of the composite film was discussed. The surface morphology, chemical compositions, and hydrophobicity of the composite film on the glass substrate were investigated by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and water contact angle (water CA) measurements. The results indicated that the composite film exhibited stable superhydrophobicity and excellent photocatalytic activity for degradation of methyl orange (MO) even after five continuous cycles of photocatalytic reaction when M/T was 7:1. The water CA and degradation efficiency for MO remained at 154° and 94%, respectively. Further, the composite film showed a good non-sticking characteristic with the water sliding angle (SA) at about 4°. The SiO₂@(TiO₂/MoS₂) composite consisting of hydrophobic SiO₂ nanoparticles and TiO₂/MoS₂ heterostructure could provide synergistic effects for maintaining long-term self-cleaning performance.     

Dye sensitized CO<Subscript>2</Subscript> reduction over pure and platinized TiO<Subscript>2</Subscript>

TiO₂ thin and thick films promoted with platinum and organic sensitizers including novel perylene diimide dyes (PDI) were prepared and tested for carbon dioxide reduction with water under visible light. TiO₂ films were prepared by a dip coating sol–gel technique. Pt was incorporated on TiO₂ surface by wet impregnation [Pt(on).TiO₂], or in the TiO₂ film [Pt(in).TiO₂] by adding the precursor in the sol. When tris (2,2′-bipyridyl) ruthenium(II) chloride hexahydrate was used as sensitizer, in addition to visible light activity towards methane production, H₂ evolution was also observed. Perylene diimide derivatives used in this study have shown light harvesting capability similar to the tris (2,2′-bipyridyl) ruthenium(II) chloride hexahydrate.     

A comparative study of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> adsorption using activated carbon prepared from pine cone by phosphoric acid activation

Adsorption of pure carbon dioxide and methane was examined on activated carbon prepared from pine cone by chemical activation with H₃PO₄ to determine the potential for the separation of CO₂ from CH₄. The prepared adsorbent was characterized by N₂ adsorption-desorption, elemental analysis, FTIR, SEM and TEM. The equilibrium adsorption of CO₂ and CH₄ on AC was determined at 298, 308 and 318 K and pressure range of 1–16 bar. The experimental data of both gases were analyzed using Langmuir and Freundlich models. For CO₂, the Langmuir isotherm presented a perfect fit, whereas the isotherm of CH₄ was well described by Freundlich model. The selectivity of CO₂ over CH₄ by AC (CO₂: CH₄=50: 50, 298K, 5 bar), predicted by ideal adsorbed solution theory (IAST) model, was achieved at 1.68. These data demonstrated that pine cone-based AC prepared in this study can be successfully used in separation of CO₂ from CH₄.     

Effect of La as Promoter in the Photoreduction of CO<Subscript>2</Subscript> Over TiO<Subscript>2</Subscript> Catalysts

In this work, TiO₂ has been modified by treating it thermally together with different proportions (0.5–15 wt%) of La₂O₃. The resulting materials have been extensively characterized by XRD, TEM, N₂ adsorption isotherms, temperature-programmed CO₂ desorption, Raman, UV–Vis photoluminescence and X-ray photoelectron spectroscopies. The activity tests of these materials for the gas-phase photocatalytic reduction of carbon dioxide show that the main products of the reaction are in all cases CO and CH₄, together with H₂ from the parallel reduction of water. After the preparation procedure, La phases are best described as oxycarbonates, and lead to improved activity with respect to TiO₂ with La contents up to 5 wt%. Higher loadings do not, however, lead to further enhanced activity. Retarded electron–hole recombination and enhanced CO₂ adsorption are invoked as the key factors contributing to this activity improvement, which is optimized in the case of 0.5 wt% La leading to higher productions of CO and CH₄ and increased quantum efficiency with respect to titania.     

Investigation of a new lead-free Bi<Subscript>0.5</Subscript>(Na<Subscript>0.40</Subscript>K<Subscript>0.10</Subscript>)TiO<Subscript>3</Subscript>-(Ba<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>)TiO<Subscript>3</Subscript> piezoelectric ceramic

Lead-free piezoelectric compositions of the (1-x)Bi_0.5(Na_0.40K_0.10)TiO₃-x(Ba_0.7Sr_0.3)TiO₃ system (when x = 0, 0.05, 0.10, 0.15, and 0.20) were fabricated using a solid-state mixed oxide method and sintered between 1,050°C and 1,175°C for 2 h. The effect of (Ba_0.7Sr_0.3)TiO₃ [BST] content on phase, microstructure, and electrical properties was investigated. The optimum sintering temperature was 1,125°C at which all compositions had densities of at least 98% of their theoretical values. X-ray diffraction patterns that showed tetragonality were increased with the increasing BST. Scanning electron micrographs showed a slight reduction of grain size when BST was added. The addition of BST was also found to improve the dielectric and piezoelectric properties of the BNKT ceramic. A large room-temperature dielectric constant, ε _r (1,609), and piezoelectric coefficient, d ₃₃ (214 pC/N), were obtained at an optimal composition of x = 0.10.     

Photoconducting and Photovoltaic Properties of ZnO:TiO<Subscript>2</Subscript> Composite/p-Silicon Heterojunction Photodiode

A photodiode based on titanium dioxide:zinc oxide (TiO₂:ZnO) was fabricated to be used in optoelectronics applications. The TiO₂:ZnO composite film was prepared by the sol-gel method. The structural properties of the composite film were analyzed by scanning electron microscopy and X-ray diffraction techniques. It is seen that the film is formed from the nanoparticles. The photoresponsivity properties of the TiO₂:ZnO composite film/p-type silicon diode were analyzed by phototransient current and photocapacitance techniques. The diode exhibited an optoelectronic device with obtained photovoltaic and photocapacitance behaviors. It is evaluated that the TiO₂:ZnO composite film/p-type silicon diode can be used as a optoelectronic device in optic communications and photoelectric applications.     

Detection of CO<Subscript>2</Subscript> and O<Subscript>2</Subscript> by iron loaded LTL zeolite films

Detection of oxygen and carbon dioxide is important in the field of chemical and biosensors for atmosphere and biosystem monitoring and fermentation processes. The present study reports on the preparation of zeolite films doped with iron nanoparticles for detection of CO₂ and O₂ in gas phase. Pure nanosized LTL type zeolite with monomodal particle size distribution loaded with iron (Fe-LTL) was prepared under hydrothermal condition from colloidal precursor suspensions. The zeolite was loaded with iron to different levels by ion exchange. The Fe-LTL suspensions were used for preparation of thin films on silicon wafers via spin coating method. The reduction of the iron in the zeolite films was carried out under H₂ flow (50% H₂ in Ar) at 300 °C. The presence of iron nanoparticles is proved by in situ ultra-violet-visible spectroscopy. The properties of the films including surface roughness, thickness, porosity, and mechanical stability were studied. In addition, the loading and distribution of iron in the zeolite films were investigated. The Fe-LTL zeolite films were used to detect O₂ and CO₂ in a concentration dependent mode, followed by IR spectroscopy. The changes in the IR bands at 855 and 642 cm^–1 (Fe?O?H and Fe?O bending vibrations) and at 2363 and 2333 cm^–1 (CO₂ asymmetric stretching) corresponding to the presence of O₂ and CO₂, respectively, were evaluated. The response to O₂ and CO₂ was instant, which was attributed to great accessibility of the iron in the nanosized zeolite crystals. The saturation of the Fe-LTL films with CO₂ and O₂ at each concentration was reached within less than a minute. The Fe-LTL films detected both oxygen and carbon dioxide in contrast, to the pure LTL zeolite film.

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Photocatalytic Activity of a TiO<Subscript>2</Subscript> Photocatalyst Doped with C<Superscript>4+</Superscript> and S<Superscript>4+</Superscript> Ions Having a Rutile Phase Under Visible Light

C⁴⁺ and S⁴⁺-codoped titanium dioxide (TiO₂) having a rutile phase was prepared. By doping C⁴⁺ and S⁴⁺ ions into a TiO₂ lattice, the absorption edge of rutile TiO₂ powder was largely shifted from 400 to 700 nm. 2-Methylpyridine and methyleneblue were photocatalytically oxidized at high efficiency on C⁴⁺ and S⁴⁺-doped TiO₂ under visible light at a wavelength longer than 5 nm.     

Electrochemical synthesis,characterization and application of a microstructure Cu<Subscript>3</Subscript>(BTC)<Subscript>2</Subscript> metal organic framework for CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> separation

The electrochemical route is a promising and environmentally friendly technique for fabrication of metal organic frameworks (MOFs) due to mild synthesis condition, short time for crystal growth and ease of scale up. A microstructure Cu₃(BTC)₂ MOF was synthesized through electrochemical path and successfully employed for CO₂ and CH₄ adsorption. Characterization and structural investigation of the MOF was carried out by XRD, FE-SEM, TGA, FTIR and BET analyses. The highest amount of carbon dioxide and methane sorption was 26.89 and 6.63 wt%, respectively, at 298 K. The heat of adsorption for CO₂ decreased monotonically, while an opposite trend was observed for CH₄. The results also revealed that the selectivity of the developed MOF towards CO₂ over CH₄ enhanced with increase of pressure and composition of carbon dioxide component as predicted by the ideal adsorption solution theory (IAST). The regeneration of as-synthesized MOF was also studied in six consecutive cycles and no considerable reduction in CO₂ adsorption capacity was observed.     

The Synthesis and Photocatalytic Properties of Nitrogen Doped TiO<Subscript>2</Subscript> Films Prepared Using the AC-PLD Method

Synthesis of N doped TiO₂ films were conducted by the atmospheric controlled pulsed laser deposition (AC-PLD) method to generate visible light active photocatalytic films. In this method, the anion doped TiO₂ films were synthesized on a quartz substrate by the irradiation of a pulsed Nd:YAG laser on a TiO₂ target in the presence of gaseous nitrogen containing reagents at reduced pressure. For nitrogen doping, the use of CH₃CN was found to be more effective than the use of NH₃. The visible light absorption properties of the films were very sensitive to the CH₃CN partial pressure during ablation. When using CH₃CN, nitrogen and an equal quantity of carbon was uniformly doped into the TiO₂ films. The resultant films showed better catalytic performance than those which were either un-doped or doped using NH₃. The formation of nitrogen doped TiO₂ is discussed by relating experimental results to thermodynamic considerations. It is also suggested that stronger reducing agents such as carbon are required for doping nitrogen into TiO₂ films.     

Uniform color coating of multilayered TiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> films by atomic layer deposition

Thin film optics, based on light interference characteristics, are attracting increasing interest because of their ability to enable a functional color coating for various applications in optical, electronic, and solar industries. Here, we report on the dependence of coloring characteristics on single-layer TiO₂ thicknesses and alternating TiO₂/Al₂O₃ multilayer structures prepared by atomic layer deposition (ALD) at a low growth temperature. The ALD TiO₂ and Al₂O₃ thin films were studied at a low growth temperature of 80°C. Then, the coloring features in the single-layer TiO₂ and alternating TiO₂/Al₂O₃ multilayers using both the ALD processes were experimentally examined on a TiN/cut stainless steel sheet. The Essential Macleod software was used to estimate and compare the color coating results. The simulation results revealed that five different colors of the single TiO₂ layers were shown experimentally, depending on the film thickness. For the purpose of highly uniform pink color coating, the film structures of TiO₂/Al₂O₃ multilayers were designed in advance. It was experimentally demonstrated that the evaluated colors corresponded well with the simulated color spectrum results, exhibiting a uniform pink color with wide incident angles ranging from 0° to 75°. This article advances practical applications requiring highly uniform color coatings of surfaces in a variety of optical coating areas with complex topographical structures.     

Separation characteristics of tetrapropylammoniumbromide templating silica/alumina composite membrane in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>, CO<Subscript>2</Subscript>/H<Subscript>2</Subscript> and CH<Subscript>4</Subscript>/H<Subscript>2</Subscript> systems

Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al₂O₃/ α-Al₂O₃ composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO₂/N₂, CO₂/H₂ and CH₄/H₂ systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al₂O₃ support and nanoporous unsupport (TPABr templating SiO₂/ γ-Al₂O₃ composite layer without α-Al₂O₃ support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al₂O₃ support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO₂ and CH₄. While the adsorption rates in the unsupport showed in the order of H₂> CO₂> N₂> CH₄ at low pressure range, the permeate flux in the membrane was in the order of H₂≫N₂> CH₄> CO₂. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO₂/H₂ and CH₄/H₂ systems. Although light and non-adsorbable molecules, such as H₂, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO₂ and CH₄, showed a higher separation factor (CO₂/H₂=5-7, CH₄/H₂=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

The catalytic effect of both oxygen-bearing functional group and ash in carbonaceous catalyst on CH<Subscript>4</Subscript>-CO<Subscript>2</Subscript> reforming

A kind of new catalyst—carbonaceous catalyst—for CH₄-CO₂ reformation has been developed in our laboratory. The effect of both oxygen-bearing functional group such as phenolic hydroxyl, carbonyl, carboxyl, and lactonic, and ash such as Fe₂O₃, Na₂CO₃, and K₂CO₃ in the carbonaceous catalyst on the CH₄-CO₂ reforming has been investigated with a fixed-bed reactor. It has been found that the carbonaceous catalyst is an efficient catalyst on CO₂-CH₄ reforming. With the decrease of oxygen-bearing functional group, the catalytic activity of carbonaceous catalyst decreases quickly. The oxygen-bearing functional groups play a significant role in the carbonaceous-catalyzed CO₂-CH₄ reforming; the ash components in carbonaceous catalyst also have an important influence on the CO₂-CH₄ reforming. Fe₂O₃, Na₂CO₃, and K₂CO₃ in the ash can catalyze the CO₂-CH₄ reforming reaction; CaO has little effect on CO₂-CH₄ reforming reaction. CaO can catalyze the gasification between carbonaceous catalyst and CO₂; Al₂O₃ and MgO inhibit the CO₂-CH₄ reforming.     

Electrochemical preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite film and its high activity toward the photoelectrocatalytic degradation of methyl orange

Uniform TiO₂/SiO₂ composite films were prepared on ITO substrates by electrodeposition, and highly photoelectrocatalytic (PEC) activity of the composite films was observed toward the degradation of methyl orange (MO) in aqueous solutions. It was further found that their PEC activity was dependent on the electrodeposition parameters including deposition time, solution pH and SiO₂ content. Under the optimized condition, the PEC degradation of MO on TiO₂/SiO₂ composite film electrode could be enhanced about 14 times relative to that on neat TiO₂ film electrode. The high PEC activity of the TiO₂/SiO₂ composite film electrode was mainly attributed to the enhancement of the charge separation of photo-generated electron-hole pairs by the dispersion of SiO₂ nanoparticles in the TiO₂ matrix with the aid of the applied electric field.     

Li<Subscript>2</Subscript>Cu<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> + SiO<Subscript>2</Subscript>/Ti compositions for the catalytic afterburning of diesel soot

Two methods were used to obtain a catalytically active oxide coating on the surface of titanium for the catalytic afterburning of diesel soot: plasma electrochemical formation of an oxide film on the surface of titanium and extraction pyrolytic deposition of the Li₂Cu₂(MoO₄)₃ compound. The Li₂Cu₂(MoO₄)₃/TiO₂ + SiO₂/Ti compositions synthesized by the single-step extraction pyrolytic treatment of the oxidized surface of titanium ensured a high burning rate of soot of ∼300°C. The subsequent deposition of Li₂Cu₂(MoO₄)₃ lowers the activity of the catalyst, due probably to the growth of molybdate phase crystallites and the filling of open oxide film pores. Double lithium-copper molybdate is able to reduce appreciably the concentration of CO in the oxidation products of soot. The advantages of these methods are the possibility of forming high-cohesion durable coatings on surfaces of any complexity, the simplicity of their implementation, and high productivity and low cost. The obtained results can be recommended for use in developing methods for creating composite coatings on catalytic soot filters.     

Removal of atrazine by photoelectrocatalytic process under sunlight using WN-codoped TiO<Subscript>2</Subscript> photoanode

The present study was focused on the degradation of Atrazine (ATZ) and major by-products (DEA, DIA, DEDIA and ATZ-OH) from water by photoelectrocatalytic (PEC) oxidation process under solar light. The undoped TiO₂, sub-stoichiometric TiO₂ (TiO_2?x) and codoped TiO₂ (TiO₂:WN) photoanodes were prepared by means of a radio frequency magnetron sputtering (RF-MS) deposition process. The X-ray photoelectron spectra (XPS) analysis shows that the N and W atoms were incorporated into the O and Ti lattice sites of TiO₂ respectively (case of TiO₂:WN film), while the XPS measurements of the TiO_2?x films composition was determined to be TiO_1.9. The UV–Vis transmittance spectra shows that in the case of the TiO₂:WN films, the presence of nitrogen and tungsten improve the optical response of TiO₂ under visible range compare to the presence of oxygen vacancies in to the TiO_2?x films. The experimental results under solar light with an initial concentration of ATZ (100 µg L^?1) show that after 180 min of treatment, the degradation of ATZ were 34.98%, 68.57% and 94.33% using TiO₂, TiO_2?x and TiO₂:WN photoanodes, respectively. These results of ATZ degradation proved that TiO₂:WN photoanode was more photoactive under solar light. The evolution by-products of ATZ under sunlight show that the principal mechanism of ATZ degradation was the oxidation of alkyl side chain and dealkylation.

Graphical abstract

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3D Hierarchical Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> Nanostructures by Polyvinylpyrrolidone (PVP) and Chloride Ion-Assisted Synthesis and Their Photodetecting Properties

A solvothermal method has been employed to synthesize bismuth sulfide (Bi₂S₃) with three-dimensional (3D) hierarchical architectures. The influences of different types of surfactants and Cl^? species on the size and morphology were investigated. A possible formation mechanism was also proposed on the basis of time-dependent experiments. The photoresponse properties show that the conductivity of Bi₂S₃ micro-flowers is significantly enhanced and the photocurrent is approximately two orders of magnitude larger than the dark current. The response and decay times are estimated to be 142 and 151 ms, respectively. It is expected that hierarchical architectures Bi₂S₃ may provide a new pathway to develop advanced nanomaterial for high-speed and high-sensitivity photoelectrical switches and photodetecting devices.     

Electrochemical polymerization and characterization of a poly(azulene)-TiO<Subscript>2</Subscript> nanoparticle composite film

A poly(azulene)-TiO₂ composite film (PAz-TiO₂) was synthesized electrochemically by oxidation of azulene in an electrolyte medium containing TiO₂ nanoparticles. Polymerization was performed under magnetic stirring in an acetonitrile solution containing tetrabutylammonium hexafluorophosphate as the electrolyte salt. Influence of the concentration of TiO₂ in the reaction suspension on the electrochemical and optical properties and on the structure of the composite films was studied by cyclic voltammetry, ex situ Raman and FTIR reflection spectroscopy and in situ UV–vis and FTIR spectroelectrochemical techniques. Morphology of the composite films was studied by Scanning Electron Microscopy and the amount and distribution of the TiO₂ nanoparticles within the polymeric matrix by Inductively Coupled Plasma Mass Spectrometry with laser ablation. Addition of TiO₂ in the reaction suspension had a small catalytic activity for the polymerization of Az. Inclusion of TiO₂ nanoparticles in PAz did not affect the voltammetric behavior or the chemical structure of the formed polymer films. However, a different chain conformation and morphology of the film was formed when synthesized in presence of TiO₂ compared to the plain PAz film. It was also found that the film morphology was more homogeneous when the concentration of TiO₂ was ≥10 mM in the polymerization solution than films polymerized without any TiO₂.