Microwave photocatalysis III. Transition metal ion‐doped TiO2 thin films on mercury electrodeless discharge lamps: preparation,characterization and their effect on the photocatalytic degradation of mono‐chloroacetic acid and Rhodamine B

BACKGROUND: Mercury electrodeless discharge lamps (Hg‐EDLs) were used to generate UV radiation when exposed to a microwave field. EDLs were coated with doped TiO₂ in the form of thin films containing transition metal ions Mⁿ⁺ (M = Fe, Co, Ni, V, Cr, Mn, Zr, Ag). Photocatalytic degradation of mono‐chloroacetic acid (MCAA) to HCl, CO₂, and H₂O, and decomposition of Rhodamine B on the thin films were investigated in detail. RESULTS: Polycrystalline thin doped TiO₂ films were prepared by dip‐coating of EDL via a sol–gel method using titanium n‐butoxide, acetylacetone, and a transition metal acetylacetonate. The films were characterized by Raman spectroscopy, UV/Vis absorption spectroscopy, X‐ray photoelectron spectroscopy (XPS), electron microprobe analysis and by atomic force microscopy (AFM). The photocatalytic activity of doped TiO₂ films was monitored in the decomposition of Rhodamine B in water. Compared with the pure TiO₂ film, the UV/Vis spectra of V, Zr and Ag‐doped TiO₂ showed significant absorption in the visible region, and hence the photocatalytic degradation of MCAA had increased. The best apparent degradation rate constant (0.0125 min^?1), which was higher than that on the pure TiO₂ film by a factor of 1.7, was obtained with the Ag(3%)/TiO₂ photocatalyst. The effect of doping level of vanadium acetylacetonate on the photocatalytic efficiency of the V‐doped TiO₂ was determined. CONCLUSIONS: Transition metal ion‐doped TiO₂ thin films showed significant absorption in the visible region. The metal doped TiO₂ photocatalyst (with an appropriate amount of V, Zr and Ag) on the Hg‐EDLs increased the degradation efficiency of MCAA in a microwave field. Copyright © 2009 Society of Chemical Industry     

Plasmonic Effects of Infiltrated Silver Nanoparticles Inside TiO2 Film: Enhanced Photovoltaic Performance in DSSCs

The plasmonic effects of infiltrated silver (Ag) nanoparticles, with different contents, inside a nanostructured TiO₂ film on the photovoltaic performance of dye‐sensitized solar cells (DSSCs) are explored. The synthesized Ag nanoparticles are immobilized onto deposited TiO₂ nanoparticles by a new strategy using 3‐mercaptopropionic acid (MPA), a bifunctional linker molecule. Transmission electron microscope (TEM) images show that monodispersed Ag and polydispersed TiO₂ nanoparticles have an average diameter of 12 ± 3 nm and 5 ± 1 nm, respectively. Moreover, Fourier transform infrared spectroscopy (FTIR) analysis reveals that Ag nanoparticles were successfully functionalized and capped with MPA. Optical studies on the MPA‐capped Ag nanoparticles inside TiO₂ film show an increase in the total absorbance of the electrode. Moreover, EIS measurements confirm that MPA‐capped Ag nanoparticles inhibit the charge recombination and improve the stability of nanoparticles in I₃^?/I^? electrolyte. The DSSC assembled with optimal content of MPA‐capped Ag nanoparticles demonstrated an enhanced power conversion efficiency (8.82% ± 0.07%) compared with the pure TiO₂ (7.30% ± 0.05%). The increase in cell efficiency was attributed to the enhanced dye light absorption in strength and spectral range due to the surface plasmon resonance of MPA‐capped Ag nanoparticles in the photoanode.     

Visible light photocatalytic activity of TiO2/heat‐treated PVC film

BACKGROUND: Semiconductor TiO₂ has been investigated extensively due to its chemical stability, nontoxicity and inexpensiveness. However, the wide band gap of anatase TiO₂ (about 3.2 eV) only allows it to absorb UV light. TiO₂ nanoparticles modified by conditional conjugated polymers show excellent photocatalytic activity under visible light. However, these conjugated polymers are not only expensive, but also difficult to process. Polyvinyl chloride (PVC) was heat‐treated at high temperature to remove HCl and a C?C conjugated chain structure was obtained. When TiO₂ nanoparticles were dispersed into the conjugated polymer film derived from PVC, this composites film exhibited high visible light photocatalytic activity. RESULTS: The photocatalytic activity of TiO₂/heat‐treated PVC (HTPVC) film was investigated by degrading Rhodamine B (RhB) under visible light irradiation. The photodegradation of RhB follows apparent first‐order kinetics. The rate constants of RhB photodegradation in the presence of the TiO₂/HTPVC films with different mass content of TiO₂ are 16–56 and 4–14 times that obtained in the presence of the pure HTPVC and TiO₂/polymethyl methacrylate (PMMA) composite film, respectively. The TiO₂/HTPVC film showed excellent photocatalytic activity and stability after 10 cycles under visible light irradiation. CONCLUSION: TiO₂/HTPVC film exhibits high visible light photocatalytic activity and stability. Copyright © 2012 Society of Chemical Industry     

Synthesis,characterization and demonstration of self-cleaning TiO2 coatings on glass and glazed ceramic tiles

An effort was made not only to demonstrate the performance of the self-cleaning coatings on building materials such as ceramic glazed tiles and glass windows, but also to understand the fundamental issues that are still alive in the field of self-cleaning surfaces based on photocatalysis. Nano TiO₂ transparent thin films were generated by dip, spray and flow coating method. The present results indicate that the inconsistent results in the self-cleaning studies may be due to the effect of aggregation of model pollutant (methylene blue) dye on TiO₂ surface. The effect of aliovalent metal ion (Ni²⁺, Fe³⁺, Nb⁵⁺) doping on phase formation, polymorphic transition, visible light absorbance and optical transparency of TiO₂ film were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV visible absorption spectroscopy. The improved visible light activity of doped TiO₂ thin film was correlated to the Ti(Ni/Fe)O₃ phase formation, UV and visible light absorbance, variation in the optical energy band gap and the probable light scattering associated with grain size.     

Morphological and thermal properties of photodegradable biocomposite films

Biocomposites containing ultraviolet (UV) radiation absorbing inorganic nanofillers are of great interest in food packaging applications. The biodegradable polylactide (PLA) composite films were prepared by solvent casting method by incorporating 1 wt % of titanium dioxide (TiO₂) and Ag‐TiO₂ (silver nanoparticles decorated TiO₂) nanoparticles to impart the photodegradable properties. The films were exposed to UV radiation for different time periods and morphology of the composite films before and after UV exposure were investigated. The results showed that homogenous filler distribution was achieved in the case of Ag‐TiO₂ nanoparticles. The thermal properties and thermomechanical stability of the composite film containing Ag‐TiO₂ nanoparticles were found to be much higher than those of neat PLA and PLA/TiO₂ composite films. The scanning electron microscopy and X‐ray diffraction studies revealed that the photodegradability of PLA matrix was significantly improved in the presence of Ag‐TiO₂ nanoparticles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Ag-TiO2多孔薄膜及其非紫外光辐照下的超亲水特性

采用溶胶凝胶法，以钛酸丁酯为前驱体、硝酸银络合物为银源、聚乙二醇2000（PEG2000）作为结构导向剂，制备超亲水多孔Ag-TiO₂复合薄膜。用X射线衍射仪、X射线光电子能谱仪、扫描电镜、原子力显微镜表征薄膜晶相结构、化学成分以及表面形貌。根据静态水接触角、动态润湿时间、超亲水长效稳定性综合评价不同Ag含量及PEG2000添加量薄膜的超亲水性能。研究发现，掺杂Ag与PEG2000对薄膜在非紫外光下的超亲水特性具有协同作用，掺杂Ag明显提高薄膜动态润湿速度及可见光响应，表面粗糙多孔结构有利于避光条件下的长效超亲水特性。Ag含量10%、PEG2000掺杂量5%的Ag-TiO₂复合薄膜在自然光条件下已具备优良的超亲水性能；水滴0.2 s内即可在表面完全铺展到0°；避光条件下保存，超亲水时效性可达到30 d以上。在可见光活化下即可强化超亲水性能，具有良好的防雾效果。     

A Novel Method for Preparing V-doped Titanium Dioxide Thin Film Photocatalysts with High Photocatalytic Activity Under Visible Light Irradiation

The liquid phase deposition (LPD) method was successfully used for preparing V-doped TiO₂ thin film photocatalysts. In this simple and easily-controlled process, V-doped anatase TiO₂ thin films were directly deposited on a soda lime glass substrate placed in an aqueous solution containing Ti- and V-fluoro complex ions, followed by annealing. The thin films were analyzed by XRD, XPS, UV-vis. V⁴⁺ ions were introduced into the lattice of TiO₂ through in-situ substituting Ti⁴⁺. The absorption edge of V-doped TiO₂ films shifted to visible light region. The highly efficient photocatalytic activity was verified by the decomposition of methylene blue under visible light irradiation.     

Laser-Induced Silver Nanoparticles on Titanium Oxide for Photocatalytic Degradation of Methylene Blue

Silver nanoparticles doped on titanium oxide (TiO₂) were produced by laser-liquid interaction of silver nitrate (AgNO₃) in isopropanol. Characteristics of Ag/TiO₂ (Ag doped TiO₂) nanoparticles produced by the methods presented in this article were investigated by XRD, TEM, SEM, EDX, and UV-Vis. From the UV-Vis measurements, the absorption of visible light of the Ag/TiO₂ photocatalysts was improved (additional absorption at longer wavelength in visible light region) obviously. The photocatalytic efficiency of Ag/TiO₂ was tested by the degradation of methylene blue (MB) in aqueous solution. A maximum of 82.3% MB degradation is achieved by 2.0 wt% Ag/TiO₂ photocatalyst under 2 h illumination with a halogen lamp.     

Preparation of Ag nanoparticles loaded TiO2 nanoplate arrays on activated carbon fibers with enhanced photocatalytic activity

Ag loaded TiO₂ nanoplate array which grew on activated carbon fiber (ACF) was prepared in the present work. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV–Vis diffuse reflectance spectra (DRS). The photocatalytic degradation of methylene blue (MB) was used to investigate the activity of the synthesized samples. Under both UV and visible light irradiation, the Ag loaded samples showed enhanced photocatalytic activity. Besides, the effect of the deposition dosage of Ag nanoparticles on the photocatalytic activity was also investigated. Under UV light irradiation, the Ag nanoparticles acted as electron traps, which enhanced electron–hole separation efficiency of TiO₂. Under visible light irradiation, the Ag nanoparticles showed surface plasmon resonance, which induced the visible light responsive photocatalytic activity for the obtained samples.     

Excellent antimicrobial properties of mesoporous anatase TiO2 and Ag/TiO2 composite films

Optically transparent, crack-free, mesoporous anatase TiO₂ thin films were fabricated. The Ag/TiO₂ composite films were prepared by incorporating Ag in the pores of TiO₂ films with an impregnation method via photoreduction. The as-prepared composite films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectronic spectra (XPS) and N₂ adsorption. The release behavior of silver ions in the mesoporous composite film was also studied. Moreover, the antimicrobial behaviors of the mesoporous film were also investigated by confocal laser scanning microscopy. The antibacterial activities of the composite films were studied by a fluorescence label method using Escherichia coli (E. coli) as a model. The as-prepared mesoporous TiO₂ films showed much higher antimicrobial efficiency than that of glass and commercial P25 TiO₂ spinning film. The facts would result from the high surface area, small crystal size and more active sites for the mesoporous catalysis. After the doping of Ag, a significant improvement for the antimicrobial ability was obtained. To elucidate the roles of the membrane photocatalyst and the doped silver in the antimicrobial activity, cells from a silver-resistant E. coli were used. These results indicated that Ag nanoparticles in the mesoporous were not only an antimicrobial but also an intensifier for photocatalysis. The as-prepared mesoporous composite film is promising in application of photocatalysis, antimicrobial and self-clean technologies.     

Ag nanoparticles loaded TiO2/MWCNT ternary nanocomposite: A visible-light-driven photocatalyst with enhanced photocatalytic performance and stability

A visible light active photocatalyst, Ag/TiO₂/MWCNT was synthesized by loading of Ag nanoparticles onto TiO₂/MWCNT nanocomposite. The photocatalytic activity of Ag/TiO₂/MWCNT ternary nanocomposite was evaluated for the degradation of methylene blue dye under UV and visible light irradiation. Ag/TiO₂/MWCNT ternary nanocomposite exhibits (~9 times) higher photocatalytic activity than TiO₂/MWCNT and (~2 times) higher than Ag/TiO₂ binary nanocomposites under visible light irradiation. The enhancement in the photocatalytic activity is attributed to the synergistic effect between Ag nanoparticles and MWCNT, which enhance the charge separation efficiency by Schottky barrier formation at Ag/TiO₂ interface and role of MWCNT as an electron reservoir. Effect of different scavengers on the degradation of methylene blue dye in the presence of catalyst has been investigated to find the role of photogenerated electrons and holes. Simultaneously, the Ag/TiO₂/MWCNT shows excellent photocatalytic stability. This work highlights the importance of Ag/TiO₂/MWCNT ternary nanocomposite as highly efficient and stable visible-light-driven photocatalyst for the degradation of organic dyes.     

Ag/Ag2S–TiO2 composite film formed using dual phase Ag/Ag2O layer as a sulfurized layer for enhanced photocatalytic activity

The Ag/Ag₂S–TiO₂ composite films were synthesized through vulcanizing sputtering Ag/Ag₂O dural-phase template capping layer on the TiO₂ film. After hydrothermal vulcanization using thiourea as a sulfur precursor, the initially decorated Ag₂O layer transformed into the Ag₂S. The surface morphology of the continuous block structure of the Ag/Ag₂S composite layer gradually shrinks to form irregular island grains dispersed on the surface of the composite film, with vulcanization reaction duration increased from one to 3 h. The light absorption ability of the Ag/Ag₂S–TiO₂ composite film was enhanced substantially compared to the TiO₂ film because of the surface plasmon resonance effect from the Ag particles and the narrow energy band of the Ag₂S. Among various surface morphologies of the Ag/Ag₂S–TiO₂ composite films, the irregular island Ag/Ag₂S grains-decorated TiO₂ composite film presents superior photoelectrochemical and photocatalytic degradation performances than the composite films consisting of continuous block and spider-web structure of the Ag/Ag₂S decorated layers. The synergistic effects of surface plasmon resonance, Ag pathway between the semiconductors, and Z-scheme charge transfer mechanism explain the high-efficiency photocatalytic activity of the Ag/Ag₂S–TiO₂ composite films.     

Application of paraffin and silver coated titania nanoparticles in polyethylene nanocomposite food packaging films

In this work, 3% and 5% TiO₂/Ag nanoparticles were dispersed in low‐density polyethylene through melt blending process, and subsequently nanocomposite films were prepared by hot pressing. Paraffin was used for the first time in this work as compatibilizer agent. The effect of TiO₂/Ag nanoparticle content, as well as compatibilizer dosage on the antimicrobial, morphological, mechanical, and optical performance of the nanocomposite films was investigated. Improved mechanical properties of the nanocomposite films were found on using paraffin as compatibilizer in comparison with the neat low‐density polyethylene (LDPE) films. The optical study results also showed that the addition of TiO₂/Ag to the LDPE films does not drastically change the film appearance other than making them more reddish. The fabricated nanocomposites presented in this study could be a suitable choice for food packaging (subject to further investigation of the food packaging behavior). The results showed that both TiO₂/Ag nanoparticle and compatibilizer are needed to prevent the bacteria growth in the film. The best result was obtained by using 5% nanoparticle and 4% paraffin compatibilizer where the bacteria growth rate was significantly reduced by 95%. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45913.     

Photocatalytic Decomposition of Formic Acid Under Visible Light Irradiation Over V-ion-implanted TiO2 Thin Film Photocatalysts Prepared on Quartz Substrate by Ionized Cluster Beam (ICB) Deposition Method

Unique visible-light-responsive TiO₂ photocatalysts (λ>450 nm) were successfully developed by implantation of V ions into the TiO₂ thin films prepared on a quartz substrate by an ionized cluster beam (ICB) deposition method. After V ions implantation into TiO₂ thin film, the photocatalytic activity of the thin films for the decomposition of formic acid into CO₂ and H₂O was found to proceed efficiently under visible light irradiation longer than 450 nm. The TiO₂ thin film photocatalysts were characterized by XRD, UV-vis, XPS, FE-SEM and AFM.     

Rutile TiO2(101) based plasmonic nanostructures

TiO₂/Ag and TiO₂/Au nanocrystalline multilayer thin films were deposited using pulsed laser deposition technique. Investigations have been made to understand the influence of different phases of TiO₂ on the surface plasmon characteristics of the thin films. Rutile phase of TiO₂ is found to be a good host matrix for both Ag and Au nanoparticles. Compared to silver, gold nanoparticles are found to enhance the photocatalytic activity of the films by exhibiting a broad and intense absorption with a significant shift to longer wavelength region.     

Superhydrophilic Transparent Titania Films by Supersonic Aerosol Deposition

Photocatalytic and hydrophilic TiO₂ thin‐film applications include water purification, cancer therapy, solar energy conversion, self‐cleaning devices, and antifogging windows. We demonstrate superhydrophilicity of aerosol‐deposition (AD) TiO₂ films on a glass substrate without use of a carrier solvent, thereby removing the possibility of impurity contamination. AD films exhibit high visible light transmittance (greater than 80%) and superhydrophilicity (0° contact angle) with even minimal UV‐light irradiation exposure. This AD method represents a significant step toward the realization of economically viable, functional thin films for the aforementioned applications.     

An experimental and theoretical understanding of a UV photodetector based on Ag nanoparticles decorated Er-doped TiO2 thin film

Glancing angle deposition (GLAD) was employed to synthesise plasmonic Silver (Ag) nanoparticles (NPs) on the chemically prepared Erbium-doped Titanium dioxide (Er:TiO₂) thin films (TFs). The impact of using Ag NPs on the morphological, optical, and electrical aspects of Er:TiO₂ TFs were sequentially analysed. From the field emission scanning electron microscopy (FESEM) image, the Ag NPs appeared spherical and uniformly distributed on the Er:TiO₂ TFs. The size (diameter) of the maximum number of Ag NPs was ~15 nm (calculated from FESEM image). Energy dispersive X-ray (EDX) spectra assured the presence of Ag NPs on the TFs. X-ray diffraction (XRD) pattern for Ag NPs decorated Er:TiO₂ TFs closely resembled the face centred cubic crystal structure of Ag NPs and body centred tetragonal Ag–O compound. The optical spectroscopy (UV–visible diffuse reflectance and photoluminescence) elucidated that the absorption of light was significantly enhanced in the UV–visible spectral range for the TFs in which Ag NPs were sandwiched between Er:TiO₂ TF layers (Er:TiO₂/Ag NPs/Er:TiO₂). The Schottky contact-based Au/Er:TiO₂/Si photodetector (PD) and Au/Er:TiO₂/Ag NPs/Er:TiO₂/Si (plasmonic) PD were constructed. The plasmonic PD offered a better photo-responsivity of ~4.5 fold higher as compared to Er:TiO₂ TF-based PD upon 380 nm illumination under ?6 V bias. An increase in detectivity and a decrease in noise equivalent power was observed for the plasmonic device compared to Er:TiO₂ device in the UV region. A theoretical approach had been adopted to calculate the wavelength-dependent responsivity for both devices. Further, the important parameters like photoconductive gain, electron transit time and electron mobility were calculated by simulating the experimental responsivity curves of the devices. These parameters exhibited improvement in the UV regime for the plasmonic PD. The fast temporal response with short rise and decay time proves the excellent efficiency of the plasmonic UV PD.     

Visible light active Au:TiO2 nanocomposite photoanodes for water splitting: Sol–gel vs. sputtering

In this study, pure TiO₂ and Au:TiO₂ nanocomposite thin films are both synthesized using sol–gel and RF reactive co-sputtering methods. Physical and photoelectrochemical properties of the thin films deposited by each method are compared. The optical density spectra and scanning electron microscopy images of the Au:TiO₂ films reveal formation of gold nanoparticles in the all nanocomposite films synthesized by two methods. Moreover, the optical bandgap energy of the thin films decreases with addition of Au nanoparticles. X-ray photoelectron spectroscopy indicates that the presence of gold in metallic state and the formation of TiO₂ is stoichiometric. The photoelectrochemical properties of the TiO₂ and Au:TiO₂ thin films are characterized by using a compartment cell containing KOH solution as electrolyte. It is found that in the pure systems, TiO₂ sputtered films shows a higher photocurrent under visible light illumination while a reverse result is obtained for the Au:TiO₂ systems. In addition, photoirradiation on electrode/electrolyte (EE) and substrate/electrode (SE) interfaces for the sputtered samples reveals the EE illumination enhances the photoresponse of the layers as compared to SE case.     

Two-Functional Direct Current Sputtered Silver-Containing Titanium Dioxide Thin Films

The article reports on structure, mechanical, optical, photocatalytic and biocidal properties of Ti–Ag–O films. The Ti–Ag–O films were reactively sputter-deposited from a composed Ti/Ag target at different partial pressures of oxygen on unheated glass substrate held on floating potential U _fl. It was found that addition of ~2 at.% of Ag into TiO₂ film has no negative influence on UV-induced hydrophilicity of TiO₂ film. Thick (~1,500 nm) TiO₂/Ag films containing (200) anatase phase exhibit the best hydrophilicity with water droplet contact angle (WDCA) lower than 10° after UV irradiation for 20 min. Thick (~1,500 nm) TiO₂/Ag films exhibited a better UV-induced hydrophilicity compared to that of thinner (~700 nm) TiO2/Ag films. Further it was found that hydrophilic TiO₂/Ag films exhibit a strong biocidal effect under both the visible light and the UV irradiation with 100% killing efficiency of Escherichia coli ATCC 10536 after UV irradiation for 20 min. Reported results show that single layer of TiO₂ with Ag distributed in its whole volume exhibits, after UV irradiation, simultaneously two functions: (1) excellent hydrophilicity with WDCA < 10° and (2) strong power to kill E. coli even under visible light due to direct toxicity of Ag.     

Enhanced photochromism of heteropolyacid/polyvinylpyrolidone composite film by TiO2 doping

Novel composite film was synthesized by TiO₂ doping into phosphomolybdic acid (PMoA)/polyvinylpyrrolidone (PVP) system. The influence of TiO₂ doping on its microstructure and photochromic properties was investigated via atomic force microscopy, transmission electron microscope, Fourier transform infrared spectroscopy (FT‐IR), ultraviolet–visible spectra, and X‐ray photoelectron spectroscopy (XPS). After TiO₂ doping, the surface of TiO₂/PMoA/PVP composite film changed to rough from smooth, and the particle size significantly increased. The FT‐IR results verified that the basic structure of PMoA and PVP were not destroyed in the composite films. The non‐bonded interaction between the acid and polymer was strengthened by TiO₂ doping. Irradiated with UV light, composite films changed from colorless to blue. The TiO₂/PMoA/PVP composite film exhibited a strong photochromic effect and faster bleaching reaction than that of PMoA/PVP film. XPS results indicated that the amount of PMoA in photo‐reductive reaction was increased after TiO₂ doping, which resulted in the photochromic efficiencies enhanced. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41583.