Preparation of macroporous and mesoporous TiO2 film with various solvents

To investigate the effects of solvents on the microstructure, porous TiO₂ films have been prepared by sol-gel method using hydroxypropyl cellulose as the additive. Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethanol, and the mixed solution of half ethylene glycol monomethyl ether and half ethanol were chosen as the solvents. Infrared spectra, scanning electron microscope micrographs, and X-ray diffraction patterns have been studied to characterize the microstructure of the sol and film samples. The results showed that mesoporous TiO₂ films with the pore size around 20 nm, 10 nm and 6 nm were obtained when propylene glycol monomethyl ether, the mixed solution of half ethylene glycol monomethyl ether and half ethanol, and ethanol were used as solvent, respectively. It was found that COC group in the solvent was beneficial to enlarge the pore size, because the oxygen bridge in the COC groups could be pulled out and act with titanoxane polymers. When ethylene glycol monomethyl ether was used as the solvent, macroporous TiO₂ film with pore size around 200 nm was obtained. This can be ascribed to the high enough concentration of effective COC groups of the solvent.     

Controlled preparation of titania nanofilm by a template of polydopamine film and its reversible wettability

Titanium oxide (TiO₂) nanofilm was prepared by a simple method of sol-gel deposition on the glass substrate, which was pre-modified with a polydopamine (PDA) film. The as-prepared TiO₂ nanofilm was analyzed by X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The thickness of TiO₂ film can be controlled by the thickness of PDA film, which was dependent on the polymerization time. The mechanism of wettability conversion on TiO₂ film was investigated by means of contact angle measurements in different experimental conditions. The results demonstrated that humidity was the major factor for converting the hydrophobic surface of TiO₂ film into hydrophilic surface under ultra-violet (UV) irradiation. And atmospheric oxygen played dominant role in reconverting the hydrophilic surface of TiO₂ film into hydrophobic surface when it was stored in the dark. The TiO₂ nanofilm showed reversible hydrophobic/hydrophilic conversion in the condition of alternating between UV irradiation and storage in the dark.     

Structural characterization and photocatalytic activity of ultrathin TiO2 films fabricated by Langmuir-Blodgett technique with octadecylamine

TiO₂ thin films with nanometer-scale thicknesses were prepared by the hydrolysis of titanium potassium oxalate using octadecylamine (ODA) Langmuir-Blodgett (LB) films as templates. After optimizing conditions in immersion process, the amount of TiO₂ generated in the ODA LB film was found to be precisely controlled by the number of deposited ODA layers. Morphological measurements showed that uniform TiO₂ film with surface roughness of less than 1.3 nm could be prepared from the monolayer LB films through subsequent heat-treatment process, while generation of cracks became less noticeable on the 5-layer film after heat-treatment at lower holding temperature with slow heating rate. In addition, photocatalytic activities of the TiO₂ films were examined from the decomposition of cadmium stearate (CdSt) LB films and stearic acid (SA) cast films for different time intervals of irradiation with UV light. Atomic force microscopy measurements showed that an almost flat surface of the CdSt LB film changes to a moth-eaten appearance as a result of decomposition under UV light irradiation. Furthermore, the post-heat-treatment at higher temperatures resulted in decreased photocatalytic activity of the TiO₂ film for the decomposition of SA cast film.     

Thermoelectrical properties and optical third harmonic generation of Gd-doped PbTe

Nanocrystalline TiO₂ porous films were prepared by a sol-gel dip coating method from a solution using poly(ethylene glycol) as a template, ethanol as a solvent and terpineol as a highly viscous solvent. The thickness of films increases greatly by increasing the amount of terpineol. However, the overmuch incorporation of terpineol hinders the formation of porous structure and accelerates the crack creation. The crack-free film having a three-dimensionally extended porous structure was obtained at the ethanol/terpineol ratio of 8:1, the film thickness with three depositions being 2.5 μm. Pretreatment of the precursor at an appropriate temperature also plays an important role in pore formation. Single-phase anatase TiO₂ porous films were obtained after calcinations at 550°C for 1 h, and the crystal size increases with an increase in the amount of terpineol. The pore formation mechanism is discussed primarily in relation to the phase separation in the system and self-assembly of PEG.     

Rapid erasing of wettability patterns based on TiO2-PDMS composite films

TiO₂-polydimethylsiloxane (TiO₂-PDMS) composite films are prepared using the sol–gel method from a Ti(OBu)₄–benzoylacetone solution containing PDMS. The prepared films are cured by irradiation with ultraviolet (UV) light. Structural changes in the films after UV irradiation are confirmed by UV–vis absorption experiments, which show that an absorption band characteristic of the benzoylacetonate chelate rings disappears. This finding is ascribed to structural changes associated with the dissociation of the chelate rings. The IR spectra of the thin films exhibit a broad absorption band after UV irradiation, indicating that a Ti–O–Ti network forms in the thin film. Contact angles are measured for the TiO₂-PDMS thin films, showing wettability conversion from hydrophobic to superhydrophilic states by irradiation with oxygen plasma for 1 s. This phenomenon is explained by XPS experiments which reveal that the number of carbon atoms decreases, whereas the number of oxygen atoms increases on the surface of the TiO₂-PDMS composite films. Finally, hydrophobic–superhydrophilic patterns are fabricated based on a patterned TiO₂-PDMS composite film. The film displays a rapid change to superhydrophilicity over the whole film surface upon plasma irradiation for 1 s, which means that the wettability patterns are rapidly erasable.     

Preparation of nanocrystalline TiO2 porous films from terpineol-ethanol-PEG system

Nanocrystalline TiO₂ porous films were prepared by a sol-gel dip coating method from a solution using poly(ethylene glycol) as a template, ethanol as a solvent and terpineol as a highly viscous solvent. The thickness of films increases greatly by increasing the amount of terpineol. However, the overmuch incorporation of terpineol hinders the formation of porous structure and accelerates the crack creation. The crack-free film having a three-dimensionally extended porous structure was obtained at the ethanol/terpineol ratio of 8:1, the film thickness with three depositions being 2.5 μm. Pretreatment of the precursor at an appropriate temperature also plays an important role in pore formation. Single-phase anatase TiO₂ porous films were obtained after calcinations at 550°C for 1 h, and the crystal size increases with an increase in the amount of terpineol. The pore formation mechanism is discussed primarily in relation to the phase separation in the system and self-assembly of PEG.     

The microstructure and wettability of the TiOx films synthesized by reactive DC magnetron sputtering

Different chemical state of titanium oxide films were deposited on commercially pure Ti (CP Ti) by reactive DC magnetron sputtering under different oxygen flow rates to examine a possibility of their applications to endovascular stents. The chemical composition and crystal structure of the obtained films were analyzed by XPS and XRD, respectively. In dependence on the deposition parameters employed, the obtained films demonstrated different mixture of anatase TiO₂, Ti₂O₃, TiO and Ti. The wettability of the films was measured by the water contact angle variation. By formation of titanium oxide film on CP Ti, contact angle was decreased. In order to modify and control the surface wettability, the resultant TiO_x films were etched subsequently by different plasma. The wettability was influenced by etched process according to the decreased contact angle values of etched TiO_x film. Furthermore, TiO_x films became highly hydrophilic by ultraviolet (UV) irradiation, and returned to the initial relatively hydrophobic state by visible-light (VIS) irradiation. The wettability of the TiO_x film was enabled to convert between hydrophilic and hydrophobic reversibly by alternative UV and VIS irradiation. By adjusting deposition parameter and further modification process, the wettability of the TiO_x films can be changed freely in the range of 0–90°.     

由蜂窝状结构TBT/PMMA杂化膜制备有序孔结构的TiO_2膜

采用BreathFigures法制备了蜂窝状结构的TBT/PMMA前驱体膜,气相水热处理(VPH)、热裂解前驱体膜,制备了TiO2有序孔结构膜,探讨了气相水热处理、经热裂解去除前驱体膜中聚合物成分过程中结构的变化,结果表明VPH过程中TBT水解成氢化氧化钛水合物,形成完善的-Ti-O-网络结构,抵御了高温热裂解去除聚合物过程中"液态化"聚合物的影响,最终得到有序孔结构的TiO2膜.同未经水热处理而直接热裂解得到的TiO2膜相比,有序孔结构的TiO膜紫外光电化学响应显著提高,其光电流密度约为前者的3倍.     

Comparison of hydrophilic properties of TiO2 thin films prepared by sol-gel method and reactive magnetron sputtering system

This article reports on preparation, characterization and comparison of TiO₂ films prepared by sol-gel method using the titanium isopropoxide sol (TiO₂ coating sol 3%) as solvent precursor and reactive magnetron sputtering from substoichiometric TiO_2 − x targets of 50 mm in diameter. Dual magnetron supplied by dc bipolar pulsed power source was used for reactive magnetron sputtering. Depositions were performed on unheated glass substrates. Comparison of photocatalytic properties was based on measurements of hydrophilicity, i.e. evaluation of water contact angle on the film surface after UV irradiation. It is shown, that TiO₂ films prepared by the sol-gel method exhibited higher hydrophilicity in the as-deposited state but has significant deterioration of hydrophilicity during aging, compared to TiO₂ films prepared by magnetron sputtering. To explain this effect AFM, SEM and high resolution XPS measurements were performed. It is shown that the deterioration of hydrophilicity of sol-gel TiO₂ films can be suppressed if as-deposited films are exposed to the plasma of microwave oxygen discharge.     

Synthesis and photocatalytic performance of TiO<Subscript>2</Subscript> nanospheres–graphene nanocomposite under visible and UV light irradiation

In this article, we present a fast and simple method to produce TiO₂ nanospheres–graphene nanocomposite with high photocatalytic activity under visible and UV light irradiation. TiO₂ nanospheres were adsorbed on graphene in sol–gel process. First, titanium (IV) butoxide underwent hydrolysis in graphene oxide (GO) ethanol solution resulting in TiO₂ nanospheres deposition on GO. Next, the material was calcinated to generate the phase transition of TiO₂ into anatase and reduce GO to graphene. The detailed characterization of the material was performed via transmission electron microscopy, energy dispersive X-rays spectrometer, Fourier-transformed infrared spectroscopy, X-ray diffraction, and Raman spectroscopy. Interestingly, the band-gap energy of the prepared photocatalyst was drastically decreased in comparison with the commercial photocatalyst P25 from 3.05 to 2.36 eV. This influenced in the activation of the material under visible light and resulted in high photocatalytic activity in the process of phenol decomposition in visible and UV irradiation.     

Nanodomain development of semifluorinated diblock copolymeric thin films via solvent vapor annealing

The effect of solvent vapor annealing on the morphological change of poly(ethylene oxide)-b-poly(1H,1H dihydrofluorooctyl methacrylate) (PEO-b-PFOMA) micellar thin films has been studied. The time development of the nanodomain structure in PEO(5k)-b-PFOMA(10k) thin films was investigated with the vapor treatment of perfluoroalkanes. The block copolymeric thin film was initially cast from chloroform which is a good solvent for PEO. The as-cast film which has disordered morphology can be changed to ordered cylindrical morphology and at last to highly ordered morphology consisting of PEO spherical domains and PFOMA continuous phase by varying the annealing time.     

Preparation of TiO2 paste using poly(vinylpyrrolidone) for dye sensitized solar cells

The surface morphology of titanium oxide (TiO₂) films as a photoanode in dye sensitized solar cells plays a vital role in converting light to electricity. Therefore, TiO₂ films were prepared using TiO₂ paste with different compositions of poly(vinylpyrrolidone) (PVP) as a binder to optimize their physico-chemical properties. The paste was prepared with commercial TiO₂ powder mixed with acetylacetone, PVP, 4-octylphenol polyethoxylate, acetic acid and ethanol. The chemical composition remains the same for all pastes except PVP. The quantity of the PVP was optimized in such a way that it provides a thick film with a good network connection. The impact of the quantity of PVP in the TiO₂ paste was analyzed. The prepared TiO₂ film structure was characterized by X-ray diffraction. The surface morphology was analyzed by scanning electron microscopy. The electrochemical performance of the prepared TiO₂ as a photoanode was also investigated. Among the four different photoanodes, the cells fabricated with a TiO₂ film prepared with 0.4 g of PVP exhibited the highest power conversion efficiency of 6.77%, short-circuit photocurrent density and open circuit voltage of 12.38 mA/cm² and 0.77 V, respectively.     

Poly(vinyl alcohol)/poly(acrylic acid)/TiO2/graphene oxide nanocomposite hydrogels for pH-sensitive photocatalytic degradation of organic pollutants

Poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels were prepared using radical polymerization and condensation reaction for the photocatalytic treatment of waste water. Graphene oxide was used as an additive to improve the photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO₂ nanocomposite hydrogels. Both TiO₂ and graphene oxide were immobilized in poly(vinyl alcohol)/poly(acrylic acid) hydrogel matrix for an easier recovery after the waste water treatment. The photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels was evaluated on the base of the degradation of pollutants by using UV spectrometer. The improved removal of pollutants was due to the two-step mechanism based on the adsorption of pollutants by nanocomposite hydrogel and the effective decomposition of pollutants by TiO₂ and graphene oxide. The highest swelling of nanocomposite hydrogel was observed at pH 10 indicating that poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels were suitable as a promising system for the treatment of basic waste water.     

Fabrication of micro-patterned TiO2 thin films incorporating Ag nanoparticles

A photosensitive TiO₂ thin film embedded with Ag nanoparticles has been prepared from a Ti(OBu)₄–acetylacetone solution, containing dispersed Ag nanoparticles, by the sol–gel method. UV–visible absorption spectra showed that the thin film obtained has two absorption bands, characteristic of the acetylacetone chelate rings and plasmon resonance from Ag nanoparticles. After the irradiation of UV light, the absorption band from the chelate rings almost disappeared, ascribed to structural changes associated with dissociation of the chelate rings. The thin film after the UV irradiation exhibited a broad absorption band in the IR spectrum, indicating that a Ti–O–Ti network was formed in the thin film. HRTEM and EDX spectra revealed that Ag nanoparticles were present and dispersed in the TiO₂ thin film. Micro-patterns of 50 μm dots have been fabricated by UV irradiation through a corresponding photomask, followed by leaching.     

Photocatalytic degradation of methylene blue by Au-deposited TiO<Subscript>2</Subscript> film under UV irradiation

A TiO₂ photocatalytic film was prepared by the sol–gel and dip-coating methods. Au-loaded TiO₂ photocatalytic films were produced by the photodeposition method. The photocatalytic activity of the films under UV irradiation was evaluated by measuring the degradation of absorbance for a methylene blue (MB) aqueous solution. Au particles deposited on the TiO₂ film improved the photocatalytic activity under the O₂ bubbling condition. On the other hand, under N₂ or Ar bubbling, the doubly reduced form of MB, leuco-methylene blue (LMB), was formed at the beginning of UV irradiation, and then both MB and LMB were decomposed gradually by the photocatalytic reaction. In this process, Au particles on the TiO₂ film behave as electron traps.     

Enhanced Photocatalytic Property of Reduced Graphene Oxide/TiO2 Nanobelt Surface Heterostructures Constructed by an In Situ Photochemical Reduction Method

A facile method is proposed to assemble graphene oxide (GO) on the surface of a TiO₂ nanobelt followed by an in situ photocatalytic reduction to form reduced graphene oxide (rGO)/TiO₂ nanobelt surface heterostructures. The special colloidal properties of GO and TiO₂ nanobelt are exploited as well as the photocatalytic properties of TiO₂. Using water–ethanol solvent mixtures, GO nanosheets are tightly wrapped around the surface of the TiO₂ nanobelts through an aggregation process and are then reduced in situ under UV‐light irradiation to form rGO/TiO₂ nanobelt surface heterostructures. The heterostructures enhance the separation of the photoinduced carriers, which results in a higher photocurrent due to the special electronic characteristics of rGO. Compared to TiO₂ nanobelts, the rGO/TiO₂ nanobelt surface heterostructures possess higher photocatalytic activity for the degradation of methyl orange and for the production of hydrogen from water, as well as excellent recyclability, with no loss of activity over five cycles.     

Improving conversion efficiency of dye-sensitized solar cells by metal plasma ion implantation of ruthenium ions

Dye-sensitized solar cells (DSSC) are based on the concept of photosensitization of wide-band-gap mesoporous oxide semiconductors. At present, DSSC have ventured into advanced development and pilot production. Our current research emphasizes on improvements on titanium dioxide (TiO₂) photosensitivity under visible light irradiation by using metal plasma ion implantation (MPII). The anatase TiO₂ electrode was prepared via a sol-gel process and deposited onto indium-tin oxide glass substrates. Subsequently, the as-deposited TiO₂ films were subjected to MPII at 20 keV in order to incorporate ruthenium (Ru) atoms onto the TiO₂ surface layer. The Ru-implanted TiO₂ thin film possessed nanocrystalline Ru clusters of 20 nm in diameter and distributed in near surface layer of TiO₂ films. The Ru clusters showed effective in both prohibiting electron-hole recombination and generating additional Ru-O impurity levels for the TiO₂ band gap structure. A significant reduction of TiO₂ band gap energy from 3.22 to 3.11 eV was achieved, which resulted in the extension of photocatalysis of TiO₂ from UV to Vis regime. A small drop of photoelectric performance of 8% was obtained due to the incorporation of Ru atoms in the surface layer of TiO₂, a similar side effect as observed in the Fe-implanted TiO₂. However, the overall retention of the photocatalysis capability is as high as 92% when switch from UV to Vis irradiation. The improvement of the photosensitivity of TiO₂ DSSC by means of metal plasma ion implantation is promising.     

Synthesis of functional diamond-like carbon nanocomposite films containing titanium dioxide nanoparticles

Synthesis of diamond-like carbon (DLC) films with UV-induced-hydrophilicity function was studied by inductively-coupled plasma (ICP) chemical vapor deposition. Titanium tetraisopropoxide (TTIP) and oxygen gases were employed as the precursors to deposit diamond-like nanocomposite films containing titanium dioxide (TiO₂) nanoparticles. X-ray diffraction and high-resolution transmission electron microscopy revealed that TiO₂ nanocrystallites were formed in the DLC films when oxygen concentration was higher than TTIP concentration during deposition. The DLC nanocomposite film was hydrophobic without ultraviolet (UV) irradiation, and became highly hydrophilic under UV irradiation, exhibiting the self-cleaning effect. A very broad peak centered at 1580 cm^− 1 was observed in the Raman spectra confirming the formation of DLC films. The hardness of the film was about 8 GPa with a stress of 3 GPa. ICP was essential in forming the photocatalytic TiO₂ nanoparticles in the DLC matrix.     

Photo-induced formation of hydroxyapatite on TiO2 synthesized by a chemical–hydrothermal treatment

The formation of hydroxyapatite (HAp) on TiO₂ surfaces under continuous ultraviolet (UV) irradiation was investigated. Pure Ti substrates were chemically treated with H₂O₂/HNO₃ at 353 K for 20 min to form a TiO₂ gel layer. The specimens were then hydrothermally treated with an aqueous NH₃ solution in an autoclave at 453 K for 12 h. An adhesive and sufficiently crystallized anatase-type TiO₂ film could be synthesized on the Ti surface. The specimens were immersed in simulated body fluid in darkness or under UV irradiation with a centered wavelength of λ = 365 nm. Under dark conditions, a thin homogeneous HAp film was formed, with just a few spherical clusters of HAp. The UV illumination promoted the formation of HAp clusters, which may be due to the generation of functional Ti–OH or Ti–O groups on the TiO₂ surface. On the other hand, the UV light produced electron-hole pairs in the TiO₂, and the photogenerated holes that migrated to the surface repelled the Ca²⁺ ions in the solution. As a consequence, the UV irradiation suppressed the formation of a HAp thin film.     

An All Low‐Temperature Fabrication of Macroporous,Electrochemically Addressable Anatase Thin Films

Macroporous TiO₂ (anatase) thin films are fabricated by an all low‐temperature process in which substrates are dip‐coated in suspensions of mixed anatase nanoparticles and polystyrene beads, and the templating agents are removed by ultraviolet (UV) irradiation at a temperature below 50 °C. Scanning electron microscopy (SEM) and Raman spectroscopy show that the templating polymer beads are removed by UV irradiation combined with the photocatalytic activity of TiO₂. X‐Ray diffraction reveals that nanoparticle growth is negligible in UV irradiated films, while nanoparticle size increases by almost 10 times in calcined films that are prepared for comparison. The macroporous films are prepared on FTO‐(fluorine‐doped tin oxide) coated glass and ITO (indium tin oxide) coated flexible plastics and thereby used as working electrodes. In both cases, the films are electrochemically addressable, and cyclic voltammetry is consistent with the response of bulk TiO₂ for calcined films and of nanoscale‐TiO₂ for UV‐irradiated films.