Characterization and photoelectrochemical performance of Zn-doped TiO_2 films by sol-gel method

Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, photocathodic protection and photoelectrochemical properties of TiO2 thin films were investigated. It is indicated that the photoelectrical performance of the Zn?TiO2 films is enhanced with the addition of Zn element compared with the pure-TiO2 film and the largest decline by 897 mV in the electrode potential is achieved under 300 °C heat treatment. SEM?EDS analyses show that Zn element is unevenly distributed in Zn?TiO2 films; XRD patterns reveal that the grain size of Zn?TiO2 is smaller than that of pure-TiO2; FTIR results indicate that Zn - O bond forms on Zn?TiO2 surface. Ultraviolet visible absorption spectra prove that Zn?TiO2 shifts to visible light region.Mott?Shottky curves show that the flat-band potential of Zn?TiO2 is more negative and charge carrier density is bigger than that ofpure-TiO2, implying that under the synergy of the width of the space-charge layer, carrier density and flat-band potential, Zn?TiO2 with 300 °C heat treatment displays the best photocathodic protection performance.

P-Type Nitrogen-Doped ZnO Films Prepared by In-Situ Thermal Oxidation of Zn_3N_2 Films

P-type nitrogen-doped ZnO films are prepared successfully by in-situ thermal oxidation of Zn3N2 films. The prepared films are characterized by x-ray diffraction, non-Rutherford back.scattering （non-RBS） spectroscopy, x- ray photoelectron spectroscopy, and photoluminescence spectrum. The results show that the Zn3N1 films start to transform to ZnO at 400℃ and the total nitrogen content decreases with the increasing annealing temperature. The p-type fihns are achieved at 500℃ with a low resistivity of 6.33Ω.cm and a high hole concentration of ＋8.82 × 10^17 cm-3, as well as a low level of carbon contamination, indicating that the substitutional nitrogen （No） is an effective acceptor in the ZnO：N film. The photoluminescence spectra show clear UV emissions and also indicate the presence of oxygen vacancy （Vo） defects in the ZnO：N films. The p-type doping mechanism is briefly discussed.

PBST/TiO_(2)/MgO复合薄膜的制备及性能

采用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)对TiO_(2)/MgO NPs改性,采用溶液共混法制备了聚丁二酸-共-对苯二甲酸丁二醇酯(PBST)/TiO_(2)/MgO NPs纳米复合薄膜,并探讨了其在食品包装方面的应用。研究了改性TiO_(2)/MgO NPs对PBST基体机械、阻隔、抗菌和保鲜性能的影响。结果表明:复合膜的抗拉强度和水蒸汽透过率分别为29.39MPa和2.43×10^(-11) g·m/(m^(2)·s·Pa),相较PBST基体抗拉强度提高了24.32%,水蒸汽透过率降低了32.37%,且对金黄色葡萄球菌(S.aures)和大肠杆菌(E.coli)抑菌效果显著,分别达到98.7%和97.2%,并对圣女果有良好的保鲜性能,当改性后的TiO_(2)/MgO NPs质量含量为5%时,复合薄膜的性能最佳。

STUDY ON PHOTOCATALYTIC MECHANISM OF SOL-GEL-DERIVED Pb-DOPED TiO_2 THIN FILMS

Pb-doped TiO2 photocatalytic thin films were prepared on a soda-lime glass substrate via sol-gel method using TiO2 sol solution containing lead and characterized by X-ray photoelectron spectroscopy (XPS). The results showed that besides oxides of Ti(IV) there is a certain amount of oxides of To(?) and Ti(?) and Pb exists in the forms of PbTiO3 and PbO. The photocatalytic activity of the Pb-doped TiO2 films was evaluated by the photocatalytic decolorization of aqueous methyl orange and photocatalytic mechanism mas also analyzed.

Preparation and Enhanced Daylight-Induced Photo-Catalytic Activity of Transparent C-Doped TiO_2 Thin Films

The transparent C-doped TiO2 nanostructure films were fabricated on the silicate glass substrates by sol-gel spin-coated method. The as-prepared films were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, UV-visible absorption spectra （UV-vis） and X-ray photoelectron spectroscopy （XPS）. The photocatalytic activity was evaluated via the photocatalytic oxidation of methylene blue in aqueous under daylight irradiation at room temperature. The results show that the daylight-induced photocatalytic activities of the as-prepared films are improved by the C-doping. The calcination temperatures significantly affect the morphology, microstructure and photocatalytic activity of the as-prepared samples. At 723 K, the C-doped TiO2 films exhibit the highest photocatalytic activity due to the synergetic effects of good crystallization, appropriate oxygen vacancies and strong absorption in the near UV and visible-light region.

Photoelectric properties of thin Eu^(3+)-doped TiO_2 films sensitized by cis-RuL_2(SCN)_2·2H_2O

Thin nanocrystalline TiO2 films doped by europium ions (Eu3+) were obtained by the sol-gel method. The photoelectric properties of Eu3+-doped TiO2 film electrode sensitized by cis-RuL2(SCN)2·2H2O (L=cis-2,2′-bipyridine-4,4′-dicarboxlic acid) ruthenium complex were studied. The thin films were characterized by X-ray diffraction, atomic force microscopy and X-ray photoelectron spectroscopy. Effect of doping Eu3+ on microscopic structure and photoelectrical properties were discussed. The result shows that doping europium ions makes specific surface area of these films larger, which contributes to improving the photoelectric properties. It is found that an optimal composition doped with 0.2 mol.% Eu3+ exhibits the highest photoelectric properties. Isc is 0.37 mA·cm-2, which is 0.17 mA·cm-2 bigger than that of un-doped films; Voc is 405 mV, which is 50 mV bigger than that of un-doped films.

Effect of Zn and Ti mole ratio on microstructure and photocatalytic properties of magnetron sputtered TiO_2-ZnO heterogeneous composite film

Series of TiO 2-ZnO heterojunction composite films with different n（Zn）/n（Ti） ratios were prepared by UDP450 magnetron sputter ion plating equipment, and the mole ratio of Zn to Ti was controlled by adjusting the current values of sputtering target. The effects of n（Zn）/n（Ti） on the microstructures of TiO2-ZnO films were investigated by SEM, AFM, Raman and XPS, and their photocatalytic decomposition of methyl orange solutions was evaluated. The results show that an increase in n（Zn）/n（Ti） typically results in a decrease in the grain size of composite films firstly and then an increase of grain size, while an increase in n（Zn）/n（Ti） leads to an increase in film roughness firstly and then a decrease in film roughness. Both grain size and roughness of TiO2-ZnO films reach the maximum and minimum at n（Zn）/n（Ti） of 1/9.3, respectively. The n（Zn）/n（Ti） shows little effect on the valences of Zn and Ti elements, which mainly exist in the form of TiO2 and ZnO phases. The n（Zn）/n（Ti） has influence on the amount of anatase/rutile TiO2 heterojunction in the film. With increase of the n（Zn）/n（Ti）, the absorption intensity of the composite film increases and the absorption region extends to 450 nm, which is redshifted as much as 150 nm in comparison with the pure TiO2 films. However, the photocatalytic abilities of heterogeneous composite films do not depend on the n（Zn）/n（Ti） but rather on the microstructures of the TiO2-ZnO composite films. Degradation rate of the film reaches the maximum and the photocatalytic decomposition of pollutants works best when n（Zn）/n（Ti）=1：9.3.

Inverted organic solar cells with solvothermal synthesized vanadium-doped TiO2 thin films as efficient electron transport layer

We investigated the effects of using different thicknesses of pure and vanadium-doped thin films of TiO2 as the electron transport layer in the inverted configuration of organic photovoltaic cells based on poly（3-hexylthiophene） P3HT：[6-6] phenyl-（6） butyric acid methyl ester（PCBM）. 1% vanadium-doped TiO2nanoparticles were synthesized via the solvothermal method. Crystalline structure, morphology, and optical properties of pure and vanadium-doped TiO2 thin films were studied by different techniques such as x-ray diffraction, scanning electron microscopy, transmittance electron microscopy, and UV–visible transmission spectrum. The doctor blade method which is compatible with roll-2-roll printing was used for deposition of pure and vanadium-doped TiO2 thin films with thicknesses of 30 nm and 60 nm. The final results revealed that the best thickness of TiO2 thin films for our fabricated cells was 30 nm. The cell with vanadium-doped TiO2 thin film showed slightly higher power conversion efficiency and great Jsc of 10.7 mA/cm^2 compared with its pure counterpart. In the cells using 60 nm pure and vanadium-doped TiO2 layers, the cell using the doped layer showed much higher efficiency. It is remarkable that the external quantum efficiency of vanadium-doped TiO2 thin film was better in all wavelengths.

Effects of Substrate Temperature on Properties of Transparent Conductive Ta-Doped TiO_2 Films Deposited by Radio-Frequency Magnetron Sputtering

Ta-doped titanium dioxide films are deposited on fused quartz substrates using the rf magnetron sputtering technique at different substrate temperatures. After post-annealing at 550℃ in a vacuum, all the films are crystallized into the polycrystalline anatase TiO2 structure. The effects of substrate temperature from room temperature up to 350℃ on the structure, morphology, and photoelectric properties of Ta-doped titanium dioxide films are analyzed. The average transmittance in the visible region（400-800 nm） of all films is more than 73%.The resistivity decreases firstly and then increases moderately with the increasing substrate temperature. The polycrystalline film deposited at 150℃ exhibits a lowest resistivity of 7.7 × 10^-4Ω·cm with the highest carrier density of 1.1×10^21 cm^-3 and the Hall mobility of 7.4 cm^2·V^-1s^-1.

Preparation and photocatalytic activity of Cu^(2+)-doped TiO_2/SiO_2

Cu^2＋-doped nanostructured TiO2-coated SiO2 （TiO2/SiO2） particles were prepared by the layer-by-layer assembly technique and their photocatalytic property was studied. TiO2 colloids were synthesized by the sol-gel method using TiOSO4 as a precursor. The experimental results showed that TiO2 nanopowders on the surface of SiO2 particles were well distributed and compact. The amount of TiO2 increased with the increase in coating layers. The shell structure appeared to be composed of anatase titania nanocrystals at 550℃. The 2-layer coated TiO2 particles on the surface showed a higher degradation rate compared with all the different-layer samples. The photocatalytic activity of Cu^2＋-doped TiO2/SiO2 was higher than that ofundoped TiO2/SiO2. The optimum dopant content was about 0.10wt%.

Mechanism and behaviors of Cr3+-doped TiO2

TiO2 powder and TiO2 thin film on the surface of glazed ceramic tile were prepared by sol-gel method.The influences of different doping Cr3+ concentration on the photocatalytic activity of TiO2 were discussed, UV-visible and X-ray diffraction analysis were used to test the performance of TiO2 powder and film. The results indicate that photocatalytic activity of doping Cr3+-TiO2 thin film is higher than that of powder, and the interaction between Cr3+-doped and substrate can greatly enhance the photocatalytic activity. The results of X-ray diffraction and photoabsorption show that the Cr3+ -doped energy level in TiO2 is 0. 62 eV high from the top of valence band, which belongs to the type of deep energy level doping. On the basis of the semiconductor energy level theory and Cr3+ dopant energy level, the semiconductor energy level model of Cr3+ in TiO2 powder and thin film were established, and the doping mechanisms of Cr3+-doped in TiO2 powder and thin film were analyzed.

Preparation and Characterization of Nano-ZnFe_2O_4/TiO_2 Films

The nano-ZnFe2O4/TiO2 films possess the functions of desulfurization and degradation for organic pollutants. The sols of ZnFe2O4/TiO2 were prepared by sol-gel method and coated on glass and porous ceramic by vertical coating and dipping-lift processes, respectively, and the samples were obtained after drying and sintering. The composition, appearance, absorption spectrum of the films, and the influence of the film on porous ceramic performances were analyzed using SEM, AFM, UVVis spectrometer, and mercury porosimeter, respectively, to determine the operation parameters of the multifunction porous ceramic elements for gas-purification.

Zn^(2+)掺杂TiO_2纳米粉体的结构特性及光催化活性

利用酸催化的Sol-gel法制备纯的和不同掺杂量的Zn2+掺杂TiO2纳米粉体,并用XRD、BET、XPS、SPS等技术对样品进行表征.考察Zn2+掺杂量和焙烧温度对样品的光催化降解亚甲基蓝活性、相结构、晶粒尺寸和表面织构特性的影响,并结合表面光电性质和表面组成等探讨Zn2+掺杂对纳米TiO2光催化活性的影响机制.结果表明:适量掺杂Zn2+可以提高纳米TiO2的光催化活性;当Zn2+掺杂量为0.75%,焙烧温度为500℃时,制备的Zn2+掺杂TiO2纳米粉体的光催化活性最佳.Zn2+掺杂TiO2纳米粉体的光催化活性的提高应归功于Zn2+掺杂促进了光生电子和空穴的分离,抑制相变和晶粒长大从而增强光生e-/h+的氧化还原能力,增加表面羟基,改善样品表面的吸光性能.

Preparation and characterization of ZrO_2/TiO_2 composite photocatalytic film by micro-arc oxidation

ZrO2/TiO2 composite photocatalytic film was produced on the pure titanium substrate using in-situ Zr（OH）4 colloidal particle by the micro-arc oxidation technique and characterized by scanning electron microscope （SEM）, energy dispersive X-ray （EDX）, X-ray diffraction （XRD） and ultraviolet-visible （UV-Vis） spectrophotometer. The composite film shows a lamellar and porous structure which consists of anatase, futile and ZrO2 phases. The optical absorption edge of film is shifted to longer wavelength when ZrO2 is introduced to TiO2. Furthermore, the photocatalytic reaction rate constants of degradation of rhodamine B solution with ZrO2/TiO2 composite film and pure TiO2 film under ultraviolet irradiation are measured as 0.0442 and 0.0186 h 1, respectively.

Zn-TiO_2/AC复合催化剂的制备及其光催化活性

以硝酸锌、钛酸四丁酯和活性炭为原料,采用真空吸附法制备了不同组成的Zn TiO2/AC.通过X射线衍射(XRD)和透射电镜(TEM)对催化剂进行了表征.选择较难降解的Cl3CCOOH作为探针分子考察了其光催化活性.结果表明,掺锌能提高TiO2/AC的催化活性,当Zn的摩尔分数为0.5%(相对TiO2)、处理温度为400℃,溶液的pH值为6时,Zn TiO2/AC催化剂具有很好的光催化活性.

MS(M=Cd或Zn)纳米粒子负载TiO_2纳米线的制备及可见光催化性能

以具有层状结构的钛酸盐纳米线、CdCl2或ZnSO4及硫代乙酰胺为原料,采用两步水热合成法制备了高温稳定的六方相CdS或低温稳定的立方相ZnS纳米粒子负载的TiO2纳米线复合材料。首先,CdCl2或ZnSO4与钛酸盐纳米线在水热条件下进行离子交换制得含Cd2+或Zn2+的钛酸盐纳米线;然后,在硫代乙酰胺溶液中于160℃下直接处理含Cd2+或Zn2+的钛酸盐纳米线就可获得负载有硫化物纳米粒子的TiO2复合纳米线。它们在酸浸后,TiO2纳米线的表面仍存在少量硫化物纳米粒子。通过测试酸浸后样品、纯TiO2纳米线和商用P25对亚甲基蓝水溶液的可见光催化降解实验结果证实,含CdS纳米粒子样品的光催化活性最高。

改性累托石负载Zn-TiO_2复合催化剂的制备及其光催化性能的研究

以碳酸钠对累托石进行改性,并以改性后的累托石为载体,通过溶胶-凝胶法合成改性累托石负载Zn-TiO_2的复合催化剂。采用X射线衍射(XRD)仪、扫描电子显微镜(SEM)、傅立叶红外变换光谱(FTIR)仪、比表面积和孔隙分析仪对催化剂进行表征,研究煅烧温度和Zn掺杂量对催化活性的影响。通过氧化基团捕获实验和复合催化剂重复使用实验,研究了复合催化剂催化氧化酸性大红3R的催化机制和稳定性。结果表明,合成的最优复合催化剂煅烧温度为500℃,Zn掺杂量为0.8%(质量分数),在光照时间为90min时对酸性大红3R的降解率达到100%左右。重复使用3次后,酸性大红3R的降解率下降到78.23%。负载Zn-TiO_2后改性累托石的层状结构变为了片状结构。采用改性累托石作为载体时,其煅烧温度不宜超过700℃。酸性大红3R的降解是以羟基自由基氧化为主,超氧自由基氧化和抑制光生电子-空穴的重新复合为辅的共存氧化机制。

Synthesis of Cu_2ZnSnS_4 thin film from mixed solution of Cu_2SnS_3 nanoparticles and Zn ions

The Cu2ZnSnS4 thin film was prepared by a facile solution method without vacuum environment and toxic substance. The formation mechanism of the film was studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and Raman scattering measurements. Through cyclic voltammetry and photo-electricity tests, the electrocatalytic activity of the prepared film as the counter electrode of dye-sensitizedsolar cell was also studied. The results show that the mixed precursor solution mainly consists of Cu2SnS3 nanoparticles and Zn ions.After 550 °C annealing process on the precursor film prepared from the mixed solution, Cu2ZnSnS4 thin film is obtained. Besides, itis found that the prepared Cu2ZnSnS4 thin film has the electrocatalytic activity toward the redox reaction of I3?/I? and the dye-sensitized solar cell with the prepared Cu2ZnSnS4 thin film as the counter electrode achieves the efficiency of 1.09%.

Zn(Ⅱ)和La(Ⅲ)共掺杂TiO_2纳米晶多孔膜电极光电化学行为研究

采用溶胶-凝胶法合成了Zn(Ⅱ)、La(Ⅲ)共掺杂TiO2纳米粒子(掺杂0.5%Zn(Ⅱ)及0.5%La(Ⅲ)),并制成了TiO2、掺杂0.5%Zn(Ⅱ)及共掺杂0.5%Zn(Ⅱ)和0.5%La(Ⅲ)的TiO2纳米晶多孔膜电极,对该3种电极进行了电化学及光电化学研究,实验发现,用Zn(Ⅱ)单独掺杂TiO2纳米多孔膜电极的光电流大于未掺杂的TiO2纳米多孔膜电极,而Zn(Ⅱ)和La(Ⅲ)共掺杂TiO2纳米多孔膜电极的光电流又大于Zn(Ⅱ)单独掺杂TiO2纳米多孔膜电极,对该掺杂电极的光电转换机理进行了探讨。

Photoelectrocatalytic reduction of CO_2 into formic acid using WO_(3-x)/TiO_2 film as novel photoanode

A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer（XRD）, scanning electron microscope（SEM） and transmission electron microscope（TEM）. The existence of oxygen vacancies in the WO3-x was confirmed with an X-ray photoelectron spectroscopy（XPS）, and the accurate oxygen index was determined by a modified potentiometric titrimetry method. After 3h of photoelectrocatalytic reduction, the formic acid yield of the WO3-x/TiO2 film is 872 nmol/cm^2, which is 1.83 times that of the WO3/TiO2 film. The results of PEC performance demonstrate that the introduction of WO3-x nanoparticles can improve the charge transfer performance so as to enhance the performance of PEC reduction of CO2 into formic acid.