FT-IR study of the photocatalytic degradation of gaseous toluene over UV-irradiated TiO2 microballs: enhanced performance by hydrothermal treatment in alkaline solution

In this study, photocatalysts of TiO₂ microballls were obtained via a hydrothermal treating of commercial P25 in alkaline solution, and then characterized with SEM, XRD, BET, DRS and surface photovoltage spectroscopy (SPS) techniques. The photovoltage response of the prepared TiO₂ microballs on spectrum features a quantum size effect brought about by the reduced grain size with respect to the precursor. The UV-assisted photodegradation of gaseous toluene over P25 and the prepared TiO₂ microballs was monitored by an in situ infrared technique. The results demonstrated that the prepared TiO₂ microballs in anatase form were more active than commercial P25 in photocatalytic oxidation of gaseous toluene. The promoted activity of the hydrothermal-treated TiO₂ is attributed to the increasing specific surface area and larger band gap induced by the reduced crystallite size.     

Controlled synthesis of TiO2-B nanowires and nanoparticles for dye-sensitized solar cells

Controllable synthesis of the TiO₂-B nanowires (NWs) and nanoparticles (NPs) had been achieved via a facile hydrothermal route, respectively, only by tuning the solution volume. The dye-sensitized solar cells prototypes had been fabricated using TiO₂-B NW and NP electrodes, respectively. The TiO₂-B NP cells had higher photocurrent and photoelectrical conversion efficiency than the TiO₂-B NW cells though the latter exhibited larger photovoltage compared to the former. The key factors such as the photogenerated electron injection drive force, surface defects and the interfacial charge transfer, which determined the photoelectrical properties, had been systematically researched with the surface photovoltage spectra (SPS) and the electrochemical impedance spectra (EIS). The SPS proved that there was larger photoelectron injection drive force in TiO₂-B NP photoelectrode than that in NW photoelectrode. And the electrochemical impedance spectra (EIS) revealed that TiO₂-B NP cells had faster interface charge transfer compared to TiO₂-B NW cells. Both proved that NP cells had the higher photocurrents.     

Highly sensitive room-temperature gas sensors based on hydrothermal synthesis of Cr2O3 hollow nanospheres

This paper reports that Cr₂O₃ hollow nanospheres（HNs） were synthesized via a hydrothermal approach and characterized by scanning electron microscopy,x-ray powder diffraction,transmission electron microscopy（TEM）,selective area electron diffraction and high resolution TEM,respectively.In addition,the room-temperature（RT） gas sensing properties of Cr2O3 HNs and conventional powders（CPs） were investigated by means of the surface photovoltage technique.The experimental data demonstrate that the RT gas sensor of the as-fabricated HNs reaches below 5 ppm whereas that of the CPs is about 40 ppm,which results from there being much more adsorbed and desorbed oxygen in HNs than in CPs at RT.The as-prepared Cr₂O₃ HNs could have potential applications as RT nanosensors.     

Hydrothermal preparation and photoluminescence of bundle-like structure of ZnWO4 nanorods

ZnWO₄ nanorods with a bundle-like structure were synthesized at 180°C for 12 h by a hydrothermal technology from Na₂WO₄⋅2H₂O and ZnSO₄⋅7H₂O in the presence of sodium dodecyl sulfate (SDS). The as-synthesized bundle-like structure of ZnWO₄ nanorods was characterized by various techniques: TEM, XRD and EDS. The luminescence properties of the bundle-like structure of the ZnWO₄ nanorods were investigated by photoluminescence (PL) spectroscopy.     

DBS包覆TiO2纳米粒子的表面光伏及光致发光性能

采用溶胶-水热法合成了十二烷基苯磺酸钠(DBS)包覆的TiO2纳米粒子,并利用X射线衍射仪、透射电镜、表面光电压谱(SPS)和光致发光光谱(PL)等对样品进行表征.重点探讨了DBS包覆的适宜条件及DBS包覆对TiO2光伏和发光等性质的影响.结果表明,进釜前pH值在4.5~5.5,DBS用量为TiO2质量的1.0%~3.0%时,能够获得理想包覆.在水热过程中,DBS的引入对锐钛矿型TiO2微晶的生长有抑制作用.由于DBS的包覆,使TiO2的SPS和PL信号强度显著下降,这可能与磺酸基的吸电子性以及表面缺陷等的减少有关.     

A study on photo-generated charges property in highly ordered TiO2 nanotube arrays

In this study TiO₂ nanotube arrays were fabricated by potentiostatic anodization of titanium sheet. The X-ray diffraction (XRD) pattern and field emission scanning electron microscopy (FE-SEM) image indicated the TiO₂ nanotube arrays were of pure anatase form and highly ordered. The properties of the photo-generated charges in the nanotube arrays were investigated by transient photovoltage (TPV) technique and surface photovoltage (SPV) technique based on lock-in amplifier with dc bias, in comparison with the commercial powder derived film. The separation processes of the photo-induced charges in the system of TiO₂ nanotubes on Ti have been demonstrated to be correlated with the incident light intensity, surface trapping states, and the interfacial electric field between Ti and TiO₂. The results also show that the highly ordered nanotube film could generate much stronger SPV responses under external electric field than the commercial powder derived film.     

Surface electronic properties of sulfur-treated GaAs determined by surface photovoltage measurement and its computer simulation

The Kelvin method together with the simulations of surface photovoltage has been used to determine the surface electronic properties, i.e. the surface band bending (qV_S), surface state density (N_SS0) and surface fixed charge (Q_Fx) of S₂Cl₂-treated GaAs (100) surfaces. The measured values of surface photovoltage (SPV) do not show saturation at high photon flux densities in contradiction to the simple theory of SPV. This behavior of SPV agrees very well with the rigorous computer simulations and can be explained in terms of the Dember effect. Moreover, the SPV values become insensitive to surface states at moderate photon flux densities. On this basis, the surface band bending of untreated (0.79 eV) and S₂Cl₂-treated (0.60 eV) GaAs surfaces was determined. The band diagrams summarizing the obtained results proved the influence on the potential variations not only from the ionized surface states and surface fixed charge but also from the surface dipole layer on the S₂Cl₂-treated GaAs surface. The dipole arises most probably due to the S-Ga bonding on the surface. The presented results offer an alternative explanation for increased PL commonly observed after the sulfidation in the absence of substantial reduction in the band bending.     

Preparation of zinc tungstate nanomaterial and its sonocatalytic degradation of meloxicam as a novel sonocatalyst in aqueous solution

Zinc tungstate (ZnWO₄) was previously used as a photocatalyst. In this paper, for the first time as an sonocatalyst, the performance of ZnWO₄ for sonocatalytic degradation of meloxicam (MEL) under ultrasonic irradiation were studied. Firstly, ZnWO₄ nanomaterials were synthesized at different acidity (pH = 5, 6, 7, 8, 9) via the hydrothermal method. Utilizing SEM, XRD and EDS techniques to characterize composition and morphology of each product, the same crystal forms, but different morphologies (nano-sheet, nano-microspheres or nano-rod) of ZnWO₄ could be obtained. Secondly, the sonocatalytic activities of ZnWO₄ on degradation of MEL were studied. It was found that the degradation ratio varied with the synthetic pH values, with ZnWO₄ under synthetic pH = 6 exhibiting the best sonocatalytic performance (75.7%). While being synthesized at this pH value, ZnWO₄ nano-microspheres had the largest BET surface area (27.068 m²/g), the smallest particle size (40–60 nm) so as to provide more active sites on its surface, which were able to produce more reactive oxygen species (ROS) and holes under ultrasonic irradiation. These ROS and holes had a positive effect on the degradation of MEL into CO₂, H₂O and inorganic. Thirdly, various influential factors including ultrasonic power intensity, ultrasonic time, catalyst addition dosage, initial concentration of MEL solution and reusability of catalyst were also explored. Under the condition of 10 mg/L MEL concentration, 20 mg catalyst dosage, 120 min irradiation time, 0.278 W/cm² ultrasonic power intensity, the degradation ratio on MEL reached 75.7%. Finally, the presence of hydroxyl radical (OH) and singlet molecular oxygen (¹O₂) in the reaction was confirmed by adding ROS scavenger. The experimental results suggested that ZnWO₄ nanoparticle could be used not only as an effective photocatalyst, but also, under the condition of ultrasonic irradiation, a promising sonocatalyst for degradation of organic pollutants in aqueous media.     

Hydrothermal synthesis and photoelectric properties of BiVO4 with different morphologies: An efficient visible-light photocatalyst

Different morphologies of monoclinic BiVO₄ with smaller size were hydrothermal synthesized by simply adjusting the amount of surfactant (polyvinyl pyrrolidone PVP K30) added. The detailed field emission scanning electron microscope (FESEM) analysis revealed that the amount of PVP added could significantly affect the morphology and size of BiVO₄. Their photocatalytic activities were evaluated by the decolorization of methylene blue (MB) aqueous solution under visible-light irradiation (λ > 400 nm), and the as-prepared sample with well-assembled flower-like morphology showed a much higher photocatalytic activity due to larger specific surface area and higher separation efficiency of photo-induced carriers. The relationship between the behavior of photo-induced carriers and photocatalytic activity was studied using the surface photovoltage spectroscopy (SPS) and corresponding phase spectra.     

Characterization of optoelectronic properties of the ZnO nanorod array using surface photovoltage technique

Well-aligned ZnO nanorod array, synthesized by wet chemical bath deposition (CBD) method on conductive indium-in-oxide (ITO) substrate, was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. Surface photovoltage (SPV) technique based on a scanning Kelvin Probe system was employed to investigate the optoelectronic behavior of ZnO nanorod array. The surface photovoltage and its time-resolved evolution process are used to determine the energy level structure of the ZnO nanorod array.     

Effect of annealing on the physical properties of thermally evaporated In2S3 thin films

The structural, compositional, morphological and optical properties of In₂S₃ thin films, prepared by thermal evaporation technique and annealed in sulfur ambient at different temperatures have been investigated. The grazing incident X-ray diffraction patterns have indicated polycrystalline form and predominantly cubic structure of annealed In₂S₃ films. The scanning electron microscopy revealed textured surface with uniformly distributed grains and the grain size increased with increase of annealing temperature. The optical parameters of the films have been determined using conventional transmission and reflection spectra as well as from surface photovoltage measurements.     

Ultrasonically sprayed-on perovskite solar cells-effects of organic cation on defect formation of CH3NH3PbI3 films

Methylammonium lead iodide (CH₃NH₃PbI₃) based perovskite having low degrees of the disorder is of great interest for optoelectronic and photovoltaic applications. In this work, a layer of CH₃NH₃PbI₃ was successfully prepared using an ultrasonically sprayed-nebulous method. Changes in structural and optical properties alongside with photo-induced charge separation and transportation behavior were systematically studied. The surface photovoltage spectra reveal a significant reduction of the density of deep defect states as the organic content was increased. It was observed that the measured values of Urbach energies decrease from 33.36 to 28.24 meV as the amount of organic content was increased to an optimum value. The best perovskite solar cells obtained using the sprayed-on approach exhibited a J_sc of 16.54 mA/cm², a V_oc of 0.99 V, and a FF of 62.4, resulting in an overall PCE of 10.09%.     

Contact potential barriers and characterization of Ag-doped composite TiO2 nanotubes

Ag-doping TiO₂ composite nanotubes (Ag-TNTs) were synthesized by alkaline fusion followed by hydrothermal treatment. The microstructure and morphology of the materials were characterized by XRD, TEM, XPS, SPS (surface photovoltage spectroscopy), FISPS (electric field-induced surface photovoltage spectroscopy) and Raman spectroscopy. First-principles calculations based on density-functional theory (DFT) showed the formation of several impurity levels near the top of the valence band in the band gap (E_g) of rutile TiO₂ due to Ag doping. A “double junction” is proposed, involving a Schottky junction and p–n junction (denoted as “Ag-p–n junction”) occurring between the Ag particles and the nanotube surface, as well as forming inside TiO₂ nanotubes, respectively. The strongly built-in electric field of the junctions promotes the separation of photo-holes and photoelectrons, enhancing the photocatalytic efficiency. XRD results indicated that the composite Ag-TNTs exist as a mixture of anatase and rutile phases. XPS results showed that Ti⁴⁺ is the primary state of Ti. Raman spectral analysis of Ag-TNTs revealed the presence of a new peak at 271 cm⁻¹. The red-shift of the absorption light wavelength of Ag-TNTs was 0.16 eV (20 nm) due to a considerable narrowing of E_g by the existing impurity levels.     

Luminescence of ZnWO4 and CdWO4 thin films prepared by spray pyrolysis

Thin films of ZnWO₄ and CdWO₄ were prepared by spray pyrolysis and the structural, optical, and luminescence properties were investigated. Both ZnWO₄ and CdWO₄ thin films showed a broad blue-green emission band. The broad band of ZnWO₄ films was centered at 495 nm (2.51 eV) consisted of three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 540 nm (2.30 eV). The broad band of CdWO₄ films at 495 nm (2.51 eV) could be decomposed to three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 545 nm (2.28 eV). These results are consistent with emission from the WO₆⁶⁻ molecular complex. The luminance and efficiency for ZnWO₄ film at 5 kV and 57 μA/cm² were 48 cd/m² and 0.22 lm/w, respectively, and for CdWO₄ film the values were 420 cd/m² and 1.9 lm/w.     

Surface modification of nanocrystalline anatase with CTAB in the acidic condition and its effects on photocatalytic activity and preferential growth of TiO2

The nanocrystalline anatase TiO₂, which was synthesized by a sol-hydrothermal process in advance, has successfully modified with cetyltrimethylammonium bromide (CTAB) in the acidic condition as well as in the basic condition. On the basis of the measurements of infrared spectrum and X-ray photoelectron spectroscopy of the resulting TiO₂, together with the phase-transfer experiments, it is suggested that the modification mechanism in the acidic condition is closely related to Br⁻. Interestingly, compared with un-modified TiO₂, the modified TiO₂ exhibits high photocatalytic activity for degrading Rhodamine B (RhB) solution, especially for that modified in the acid. The enhanced photocatalytic activity of modified TiO₂ in the acid is attributed to the role that the Br⁻ can easily capture photo-induced holes and then form active Br, consequently effectively inducing photocatalytic oxidation reactions, based on the surface photovoltage responses of the resulting TiO₂. After that, a one-pot sol-hydrothermal route at the temperature as low as 80 °C is developed to directly synthesize CTAB-modified nanocrystalline TiO₂ with a little preferred growth along 〈0 0 1〉 direction, which can be easily dispersed in the organic system and possess good photocatalytic performance. This work provides a feasible strategy to further improve the photocatalytic performance of nanocrystalline anatase and to synthesize TiO₂ nanocrystals with preferential growth.     

Ethylene glycol-assisted solvothermal fabrication of ZnWO4 nanostructures with tunable size,optical properties,and photocatalytic activities

Large scale of uniform small ZnWO₄ nanocrystals and ZnWO₄ nanorods with tunable size have been fabricated in ethylene glycol (EG)-assisted solvothermal process, ZnWO₄ samples ranging in shape from tiny nanocrystals to nanorods were dependent on the volume ratio of EG and water (H₂O). The optical properties of ZnWO₄ nanocrystals and nanorods were investigated by photoluminescence (PL) spectroscopy, showing longer ZnWO₄ nanorods own the increased PL intensity in comparison with that of shorter ones and small ZnWO₄ nanocrystals. The photocatalytic performance of ZnWO₄ nanostructures was studied also, which indicated that the increased size of ZnWO₄ nanorods resulted the degradation of photocatalytic performance in aqueous solution.     

Pressure and temperature-dependent raman study of ZnWO4

Abstract

The Raman spectra of monoclinic ZnWO₄ (c⁴ _2h-space group) are reported over wide ranges of pressure (0-24GPa) and temperature (13-970 K). All 18 Raman active pho-nons are observed throughout these ranges. Combining the pressure and temperature Raman data, an identification scheme is suggested which makes possible to distinguish the internal modes (vibrations in the octahedral WO₆ units) from the external ones (pure lattice modes). All phonons harden with pressure, thus showing normal positive dω/dP slopes, and soften with temperature in the region 250 - 970 K (normal negative dω/dT slopes). However, two phonons show a change of slope sign below 300 K, resulting in small positive slopes at low temperatures. Since the pressure dependence of these two phonons is normal and linear, it is concluded that their anomalous, non-linear dependence with temperature is due to anharmonic (temperature induced) phonon interactions rather that volume expansion. It is found that ZnWO₄ remains stable throughout the pressure and temperature ranges.     

Enhanced photoelectrochemical properties of F-containing TiO2 sphere thin film induced by its novel hierarchical structure

The novel nanostructured F-containing TiO₂ (F-TiO₂) sphere was directly synthesized on the surface of Ti foil in the solution of NH₄F and HCl by one-step hydrothermal approach under low-temperature condition. The samples were characterized respectively by means of field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results showed that the F-TiO₂ sphere was hierarchical structure, which composed of porous octahedron crystals with one truncated cone, leading to a football-like morphology. XPS results indicated that F⁻ anions were just physically adsorbed on the surface of TiO₂ microspheres. The studies on the optical properties of the F-TiO₂ were carried out by UV-vis light absorption spectrum. The surface fluorination of the spheres, the unique nanostructure induced accessible macropores or mesopores, and the increased light-harvesting abilities were crucial for the high photoelectrochemical activity of the synthesized F-TiO₂ sphere for water-splitting. The photocurrent density of the F-TiO₂ sphere thin film was more than two times than that of the P25 thin film. Meanwhile, a formation mechanism was briefly proposed. This approach could provide a facile method to synthesize F-TiO₂ microsphere with a special morphology and hierarchical structure in large scale.     

NPB/Alq3 界面激子拆分研究

采用瞬态光电压技术研究了NPB和Alq₃界面激子拆分过程和拆分机理.对NPB和Alq₃组成双层结构的样品,在脉冲355nm激光照射下,测量样品的瞬态光电压信号,通过对不同结构的和有界面激子阻挡层的样品的瞬态光电压分析,并排除了ITO/有机外界面对激子拆分的影响,得出了NPB/ Alq₃界面激子拆分机理是向Alq₃ 注入电子,向NPB注入空穴. 关键词： 激子拆分 界面 瞬态光电压     

Preparation and characterization of Zn2SiO4: Mn phosphors with hydrothermal methods

Mn²⁺-doped Zn₂SiO₄ phosphors had been prepared by hydrothermal method in stainless-steel autoclaves. Effects of synthesized methods, reaction temperature, ambience of heat treatment on the structure and the luminescence properties of this silicate were studied with X-ray diffraction apparatus (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM) and fluorescence spectrum. Results show that Zn₂SiO₄ nanocrystalline can be obtained by hydrothermal method at relatively low temperatures. The absorption pattern shows an absorption edge at about 380 nm originated from ZnO crystals and two absorption bands at about 215 and 260 nm. Mn²⁺-doped Zn₂SiO₄ has a luminescence band with the wavelength at about 522 nm under 255 nm excitation, and the luminescent intensity increases after being heat treated.