Photoinduced deposition of gold nanoparticles on TiO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> nanotube films as efficient photoanodes for solar water splitting

Gold-modified TiO₂–WO₃ nanotubes with different amounts of gold were obtained by two methods; photoassisted deposition and one-step electrochemical anodizing method. The morphology, crystallinity and elemental composition were studied by FE-SEM, XRD and EDX. The photoelectrochemical performance was examined under Xe light illumination in 1 M NaOH electrolyte. Characterization of the as-prepared TiO₂–WO₃ samples indicated that sodium tungstate concentration in anodizing solution significantly influenced the morphology and photoelectrochemical activity of fabricated films. Also, photoelectrochemical characterizations show that the photocatalytic activity of Au/TiO₂–WO₃ nanotubes was improved as compared with that of bare TiO₂–WO₃ nanotubes. The experimental results showed that the photocatalytic activities of Au/TiO₂–WO₃ were significantly affected by the amount of Au nanoparticles. The amount of gold nanoparticles was effectively controlled by time of photoreduction of the chloroauric acid solution. These new photoanodes showed enhanced high photocurrent density with good stability and are a highly promising photoanodes for photocatalytic hydrogen production.     

Effect of Ti pretreatment on photoelectric properties of TiO2 layers prepared by plasma-anodic oxidation

Photoactive TiO₂ layers were formed by anodic oxidation of Ti in O₂ RF plasma under various conditions and Ti surface pretreatment. The photocurrent spectrum in 1M NaOH was used to calculate the quantum efficiency of the photocurrent production and the band-gap energy for indirect transitions. Photoelectrochemical properties of TiO₂ layers were studied on the decomposition of p-cresol water solution. The method of Ti surface pretreatment (mechanical polishing or chemical etching) has a decisive influence on the photoelectrochemical properties and the structure of the polycrystalline oxide, rutile, anatase or amorphous phase content.This study was supported by the Grant Agency for Sciences of Slovakia.     

Experimental and statistical analysis of dielectric barrier discharge plasma effect on sonochemically TiO2 coated cotton fabric using complete composite design

A single step ultrasonic biosynthesis method was used to synthesize and coat TiO₂ nanoparticles onto DBD plasma functionalized raw cotton. Titanium isopropoxide was reduced with aloe vera plant extract into TiO₂ nanoparticles. The effect of DBD plasma treatment on self-cleaning property of TiO₂ coated fabric was optimized statistically by using a complete composite design. To induce functional groups on the cotton fabric surface, the fabric was pre-treated with DBD plasma over various periods of time. The plasma exposure time, molarity of solution and ultrasonication time were optimized using complete composite design package. TiO₂ nanoparticles revealed spherical shape and anatase phase with average crystallite size of 10.46 nm. The statistically optimized plasma exposure time, molarity and sonication time was 7 min, 0.80 and 75 min, respectively. The plasma activation of fabric significantly improved the adsorption, tensile strength and self-cleaning ability of TiO₂ coated fabric.     

Photo(electro)catalytic Activity of Cu-Modified TiO2 Nanorod Array Thin Films under Visible Light Irradiation

In the present study, a two-step method was applied to synthesise Cu²⁺-modified TiO₂ nanorod array thin films for photocatalytic processes. TiO₂ nanorod array thin films were synthesised by a hydrothermal method and then modified with an ultrasonic-assisted sequential cation adsorption method. The samples were characterised by X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (DRS), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and inductively coupled plasma mass spectroscopy (ICP-MS) analysis. The photoelectrochemical properties of the samples were evaluated by linear sweep voltammetry and Mott–Schottky analysis; photocatalytic activities were tested by methylene blue degradation under visible light. The photocurrent density of the TiO₂/FTO sample modified with 50 mM Cu²⁺ solution was 26 times higher than that of the unmodified TiO₂/FTO sample. Additionally, methylene blue degradation efficiency under visible light was increased 40% with respect to the efficiency of the unmodified sample. The mechanism of the photocatalytic activity enhancement of Cu²⁺-modified TiO₂ nanorod films was discussed.     

Photoelectrochemical switch based on cis-Azobenzene chromophore modified TiO2 nanowires

Carboxylated-azobenzene chromophore modified TiO₂ nanowire composites were prepared and characterized. Photocurrent measured with monochromatic incident light irradiation results showed that azobenzene modified TiO₂ nanowire electrode had obviously higher photocurrent and broader visible light response covering range of 350-650 nm, and the wavelength position corresponding to the maximum photocurrent was red shift to about 470 nm. After alternate irradiation with UV and visible light, the azobenzene modified TiO₂ nanowire electrode exhibited obvious photoelectrochemical switching properties. Furthermore, the photocurrent under visible light irradiation was much higher than that under UV irradiation due to the cis-to-trans isomerization transformation of azobenzene chromophore.     

Surface modification of polyimide films using unipolar nanosecond-pulse DBD in atmospheric air

DBD-induced surface modification is very versatile to increase the adhesion or hydrophilicity of polymer films. In this paper, the DBD is produced by repetitive unipolar nanosecond pulses with a rise time of 15 ns and a full width at half maximum of about 30 ns. The power densities of the homogeneous and filamentary DBDs during plasma treatment are 158 and 192 mW/m², respectively, which are significantly less than that using ac DBD processing, and the corresponding plasma dose is also mild compared to AC DBD treatment. Surface treatment of polyimide films using the homogeneous and filamentary DBDs is studied and compared. The change of chemical and physical modification of the surface before and after plasma processing has been evaluated. It can be found that both surface morphology and chemical composition are modified, and the modification includes the rise of hydrophilicity, surface oxidation and the enhancement of surface roughness. Furthermore, the homogeneous DBD is more effective for surface processing than the filamentary DBD, which can be attributed to the fact that the homogeneous DBD can modify the surface more uniformly and introduce more polar functional groups.     

Review of Sn‐Doped Hematite Nanostructures for Photoelectrochemical Water Splitting

Hematite (α‐Fe₂O₃) nanostructures have been extensively studied as photoanodes for photoelectrochemical (PEC) water splitting. However, the photoactivity of pristine hematite nanostructures is limited by a number of factors, including poor electrical conductiviy and slow oxygen evolution reaction kinetics. Previous studies have shown that using tin (Sn) as an n‐type dopant can substantially enhance the photoactivity of hematite photoanodes by modifying their optical and electrical properties. Here, the recent accomplishments in using Sn‐doped hematite photoanodes for solar water splitting are highlighted.     

Some physical properties of the TiO2 semiconductor electrode

Some physical properties of n-TiO₂ single crystals have been studied by electrochemical and photoelectrochemical techniques. X-ray diffractometry confirmed the TiO₂ basic rutile type structure. For the TiO₂/0.5 N NaOH system in the dark a Tafel slope of 0.11 V/decade was observed between 0.50 and 0.61 V versus SCE, suggesting a one-electron process. The potential, at which the gaseous oxygen evolution was confirmed, was well over 2.0 V versus SCE. On the other hand the potential for oxygen evolution was markedly decreased to −0.75 V versus SCE, when the TiO₂ was illuminated. From these facts and the observation of passivation, transpassivation and current saturation an oxygen-pumping mechanism is proposed for the polarization behaviour of the TiO₂ electrode in the dark. The spectral responses of photocurrent generated from TiO₂ at 0.0 V bias versus SCE showed that the peak illumination current at 360 nm is larger than the dark current by three orders of magnitude. The band gap of TiO₂ was determined as 3.1 eV by assuming that the photoelectrolysis of water involves an indirect energy transition. An anomalous photoresponse was observed at 1.8 eV, which is due to the presence of surface states at the TiO₂/electrolyte interface.     

Fabrication, characterization and photoelectrochemical properties of Fe2O3 modified TiO2 nanotube arrays

TiO₂ nanotube (NT) arrays modified by Fe₂O₃ with high sensibility in the visible spectrum were first prepared by annealing anodic titania NTs pre-loaded with Fe(OH)₃ which was uniformly clung to the titania NTs using sequential chemical bath deposition (S-CBD). The photoelectrochemical performances of the as-prepared composite nanotubes were determined by measuring the photo-generated currents and voltages under illumination of UV-vis light. The titania NTs modified by Fe₂O₃ showed higher photopotential and photocurrent values than those of unmodified titania NTs. The enhanced photoelectrochemical behaviors can be attributed to the modified Fe₂O₃ which increases the probability of charge-carrier separation and extends the range of the TiO₂ photoresponse from ultraviolet (UV) to visible region due to the low band gap of 2.2 eV of Fe₂O₃.     

Visible photocurrent response of TiO2 anode

The photoelectrochemical response to the electromagnetic radiation over the visible range is particularly sought for from the point of view of the efficiency of hydrogen generation by water photolysis in a photoelectrochemical solar cell, PEC. The PEC used in this work comprises thin film TiO₂ - based photoanode, Pt foil covered with Pt black as a cathode and SCE as a reference electrode, immersed in an electrolyte solution. Titanium dioxide thin films are deposited by means of rf reactive sputtering and modified, when necessary, by Au or Ag ultra-thin overcoatings. Here we show that even unmodified TiO₂ photoanode, shows a photocurrent peak over the visible range of the light spectrum (λ = 500-650 nm). The effect of the surface modification by noble metals and properties of the aqueous electrolyte on the visible photocurrent are studied. The optical spectra indicate an increased absorption due to noble metal deposits at 410 nm for Ag and at 600 nm for Au. In contrast, the photocurrent peak over the visible range (500 nm < λ < 650 nm) changes its symmetry and decreases in intensity with the increasing thickness of noble metals layers. The visible photoresponse is explained in terms of OH formation at the interface between TiO₂ electrode and aqueous electrolyte.     

Investigations of Pulse‐Plasma‐Polymer Coating on TiO2 Nanoparticles and Their Dispersion

An amorphous acrylic acid (AA) polymer coating was generated on TiO₂ nanoparticles through pulse radio frequency (RF) plasma polymerization. The AA plasma synthesis mechanism was studied by its optical emission spectrum. The chemical structures of AA–plasma‐polymer were carefully investigated by Fourier transform infrared spectroscopy (FTIR). The dispersion behaviors of AA‐coated and uncoated TiO₂ nanoparticles in glycol solution were characterized by ultraviolet absorbency and particle size distribution measurements. The results showed that the aggregation of TiO₂ nanoparticles in glycol solution was effectively lowered and the dispersion was improved a lot after AA–plasma‐polymer coating. The pulse plasma coating parameters played an important role in the dispersion enhancement of TiO₂ nanoparticles. By properly regulating the pulse discharge parameters, the system could gain the highest radical–monomer reactions rate, the most compatible functional groups on the nanoparticles, and the best dispersion in the background media.     

A novel TiO2 nanoparticles/nanowires composite core with ZrO2 nanoparticles shell coating photoanode for high-performance dye-sensitized solar cell based on different electrolytes

The novel TiO₂ nanopartilces/nanowires (TNPWs) composite with ZrO₂ nanoparticles (ZNPs) shell-coated photoanodes were prepared to fabricate high-performance dye-sensitized solar cell (DSSC) based on different types of electrolytes. Hafnium oxide (HfO₂) is a new and efficient blocking layer material applied over the TNPWs-ZNPs core-shell photoanode film. TiO₂ nanoparticles (TNPs) and TiO₂ nanowires (TNWs) were characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). DSSCs were fabricated using the novel photoanodes with an organic sensitizer D149 dye and different types of electrolytes namely liquid electrolyte, ionic liquid electrolyte, solid-state electrolyte, and quasi-solid-state electrolyte. The DSSC-4 made through the novel core-shell photoanode using quasi-solid-state electrolyte showed better photocurrent efficiency (PCE) as compared to the other DSSCs. It has such photocurrent-voltage characteristics: short circuit photocurrent (Jsc)?=?19 mA/cm², the open circuit voltage (Voc)?=?650 mV, fill factor (FF)?=?65 %, and PCE (η)?=?8.03 %. The improved performance of DSSC-4 is ascribed to the core-shell with blocking layer photoanode could increased electron transport and suppressed recombination of charge carriers at the TNPWs-ZNPs/dye/electrolyte interface.     

Efficient and Rapid Synthesis of Radioactive Gold Nanoparticles by Dielectric Barrier Discharge

A compact bench‐top system based on a dielectric barrier plasma discharge (DBD), enables the rapid, automatable, and continuous‐flow synthesis of gold nanoparticles (AuNPs) and radioactive gold nanoparticles (¹⁹⁸AuNPs). AuNPs are used as radiosensitizers in oncology, and ¹⁹⁸AuNPs (half‐life: 2.7 d) have been suggested as potential cancer brachytherapy sources. Plasma applied at the surface of a liquid containing gold ions (AuCl₄^?) and dextran induces the production of AuNPs directly in water. This synthesis is monitored in real time by UV–visible spectrometry: the change of absorbance of the solution provides new insights on the growth dynamics of AuNPs by plasma synthesis. By balancing gold ions and surfactant molecules, particles with a diameter lying in the optimal range for radiosensitizing applications (28 ± 9 nm) are produced. The method yields a reduction of more than 99% of the gold ions within only 30 min of plasma treatment. A postsynthesis ripening of the AuNPs is revealed, monitored by UV–visible spectrometry, and quantified within the first few hours following plasma treatment. Radioactive ¹⁹⁸AuNPs are also produced by DBD synthesis and characterized by electron microscopy and single‐photon emission computed tomography imaging. The results confirm the efficiency of DBD reactors for AuNPs synthesis in oncology applications.     

TiO2/CdSe多层膜结构的制备及光电化学性能研究

采用电化学方法在导电的ITO/TiO₂ 薄膜上沉积了棕红色CdSe薄膜, 并制得TiO₂/CdSe多层膜体系,研究了多层膜的微结构和光电化学性能. 实验表明, CdSe薄膜沿着(111)方向择优生长, 多层膜结构的厚度和紫外-可见光吸收强度随着沉积层数的增加而增加. 通过测定多层膜电极的光电化学性能表明, 二层膜体系的开路电压和短路电流密度最大,光电化学性能最好.     

Electrostatic assembly of CdTe quantum dots with different charged ligands into TiO2 porous film for solar cells

We have demonstrated an approach for the electrostatic assembly of CdTe quantum dots (QDs) with different charged ligands as sensitizers, achieving high coverage and good dispersion in TiO₂ porous films. The CdTe QD-sensitized TiO₂ porous films were subjected to thermal annealing in a high vacuum chamber to remove the ligand linker, resulting in the formation of direct heterojunctions between the bare CdTe QDs and TiO₂ for a favorable charge transfer. The as-received CdTe QD-sensitized TiO₂ porous films were employed as photoanodes for quantum dot-sensitized solar cells (QSSCs), and the photocurrent density reached as high as 4.69 mA/cm² under a standard illumination condition of simulated AM 1.5G (100 mW/cm²).     

Nanocoral architecture of TiO2 by hydrothermal process: Synthesis and characterization

TiO₂ thin films with novel nanocoral-like morphology were successfully grown directly onto the glass and conducting fluorine doped tin oxide coated glass substrates via multi-step hydrothermal (MSH) process. Titanium chloroalkoxide [TiCl₂ (OEt)₂ (HOEt)₂)] precursor was used in an aqueous saturated NaCl in presence of 1 mM HCl catalyst and HNO₃ peptizer at 120 °C. Reaction time varied from 3 to 12 h. The morphological features and physical properties of TiO₂ films were investigated by field emission scanning electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, Fourier transform IR spectroscopy, Fourier transform Raman spectroscopy, room temperature photoluminescence spectroscopy and X-ray photoelectron spectroscopy. The surface morphology revealed the formation of TiO₂ corals having nanosized (30-40 nm) polyps. The photoelectrochemical properties of the TiO₂ nanocoral electrodes were investigated in 0.1 M NaOH electrolyte under UV illumination. The results presented in this study highlight two major findings: (i) ability to tune the photoelectrochemical response and photoconversion efficiency via controlled thickness of TiO₂ nanocorals and (ii) the substantial increase in short circuit photocurrent (J_sc) due to the improved charge transport through TiO₂ nanocorals prepared via MSH process. This approach would be quite useful for the fabrication of nanocoral architecture that finds key applications in photocatalysis, dye-sensitized solar cells and hybrid solar cells.     

Improved charge collection efficiency of hollow sphere/nanoparticle composite TiO2 electrodes for solid state dye sensitized solar cells

The photoanodes of solid state dye sensitized solar cells (ss-DSCs) embedded with different contents of TiO₂ hollow spheres (HSs) were prepared and the photovoltaic performances were systematically characterized. TiO₂ hollow spheres were synthesized by a facile sacrificial templating method, grounded and added in different ratios to TiO₂ nanoparticle (NP) paste, from which composite HS/NP electrodes were fabricated. The composite photoanodes include hollow spheres of 300–700 nm with enhanced light scattering characteristics in visible range which leads to improved light absorption in conventional thin film electrodes of ss-DSC. By optimizing the amount of HSs in the paste, 40% improvement in efficiency was obtained in comparison to ss-DSC utilized pure NP electrodes. By increasing the fraction of HSs in the electrode the current density increased by 56% (from 2.5 to 3.9 mA cm^?2). The improved photovoltaic performance of ss-DSC is primarily due to different morphology and altered charged trap distribution in HSs in comparison to NP which leads to significant enhancement in electron transport time and electron lifetime as well as charge collection efficiency and light absorption properties.     

Electron transport in dye-sensitized solar cells based on TiO2 nanowires

Anatase titanium dioxide nanowire arrays were prepared by hydrothermally oxidizing titanium foils in aqueous alkali and transferred onto fluorinated tin oxide(FTO)glass for use as the photoanodes of front side illuminated dye-sensitized solar cells(DSCs).Electrochemical impedance spectroscopy(EIS)measurement was applied to compare the electron transport and recombination properties of DSCs using TiO2nanowire films and TiO2nanoparticle films as photoanodes.It was found that the nanowire array films possess smaller electron transport resistance(Rt)and larger electron diffusion length(Le)in the photoanodes,suggesting that the nanowire arrays can enhance the electron transport rate and have a potential to improve the charge collection efficiency of DSCs.     

Influence of Gap Spacing between Dielectric Barriers in Atmospheric Pressure Discharges

The breakdown activity in helium atmospheric pressure dielectric barrier discharge (DBD) plasma is strongly modified by introducing small impurities (nitrogen (N₂) and air in ppm), although its precise implications for the behavior of discharge plasma is not evident under several constraints. In this simulation study, we investigate the influence of gap spacing between the dielectric barriers to explore the dynamic modification in the structure of discharge plasma in distinct phases of the discharge current pulse using a two‐dimensional fluid model in He‐air gas mixture. Specifically, the impact of nitrogen and air impurities is contrasted by exploring the spatial distributions of electrons in the breakdown phase under similar operating conditions. The filamentary mode of DBD plasma in He‐N₂ is transformed into uniform glow discharge in He‐air gas mixture by the dominant effect of Penning ionization. Finally, the outcomes of two‐dimensional fluid model are validated by comparing with three‐dimensional fluid model to provide the reliability of numerical simulations. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of TiO2 thin films coated on metal substrate

Nanostructured titanium dioxide (TiO₂) thin films have been prepared on metal substrates using a facile layer-by-layer dip-coating method. The phase structure and morphologies of preparing samples were characterized by means of X-ray powder diffraction (XRD) and field-emission scanning electron microscopy (FESEM). The results confirm that films are highly crystalline anatase TiO₂ and free from other phases of titanium dioxide. Scanning electron microscopy (SEM) shows that the nanoparticles are sintered together to form a compact structure. The electrical properties of samples were investigated by cutternt-voltage analysis, the result indicates that a rectifying junction between the nanocrystalline TiO₂ film and metal substrate was formed. The photoelectrochemical characteristics recorded under 1.5 AM illumination indicates that the as-fabricated thin film electrode possesses the highest photocurrent density at 450 °C, which is 1.75 mA/cm² at 0 V vs. Ag/AgCl.