In2O3敏化ZnO纳米棒阵列的性能及其光电催化活性

以掺氟SnO₂ (FTO)导电玻璃为基底, 采用水热法制备了ZnO纳米棒阵列. 通过In(NO₃)₃水溶液水洗的方法, 合成了In₂O₃敏化ZnO纳米棒阵列光催化剂. 采用场发射扫描电子显微镜(FESEM), X射线能谱(EDX), X射线衍射(XRD)及紫外-可见漫反射光谱(UV-Vis DRS)对样品的形貌、结构、组成、晶相等进行一系列的表征. 以罗丹明B (RhB)为目标降解物, 探究了In₂O₃敏化ZnO 纳米棒阵列光电催化活性. 采用场诱导表面光伏技术(FISPV)研究了不同含量的In₂O₃敏化ZnO纳米棒阵列在光照射下的光生电荷行为. 结合电化学工作站检测不同样品的光电流, 随着In₂O₃敏化量的改变, 光电流和开路电压也随之改变. 并探讨了In₂O₃敏化ZnO纳米棒阵列光生电荷行为与光电催化活性之间的关系. 结果表明, 适量In₂O₃敏化的ZnO光催化剂在可见光下2 h内对罗丹明B的降解效率达到95%, 是单纯ZnO纳米棒阵列的2.4倍.     

负偏压下Ag@AgBr/Ni膜电极光电催化降解罗丹明B的性能和机理

用电化学方法制备Ag@AgBr/Ni表面等离子体薄膜电极,以扫描电子显微镜（SEM）、X射线衍射（XRD）和紫外-可见漫反射光谱（UV-Vis DRS）对薄膜的表面形貌、晶相结构、光吸收特性进行了表征,在负偏压和可见光作用下,以罗丹明B为模拟污染物对薄膜的光催化活性和稳定性进行了测定,采用电化学技术和向溶液中加入活性物种捕获剂的方法对薄膜光电催化降解机理进行了探索。结果表明：最佳工艺下制备的Ag@AgBr/Ni膜电极是由表面沉积纳米Ag的纳米晶AgBr颗粒构成的薄膜,具有显著的表面等离子共振效应。薄膜具有优异的光电催化活性和良好的催化稳定性,在最佳负偏压和可见光照射下反应12 min,薄膜光电催化罗丹明B（c=5 mg·L^-1）的降解率是多孔TiO₂（P25）/ITO纳米薄膜的10.2倍。相对于未加偏压的光催化,降解率提高了2.0倍;在保持薄膜光催化活性基本不变的前提下可循环使用5次。电极表面纳米Ag粒子的等离子体共振对于光阴极反应（价带反应）的活化作用是光电催化活性提高的重要原因。提出了负偏压下Ag@AgBr/Ni表面等离子体薄膜光电催化降解罗丹明B的反应机理。     

负偏压下Ag@AgBr/Ni膜电极光电催化降解罗丹明B的性能和机理

用电化学方法制备Ag@Ag Br/Ni表面等离子体薄膜电极,以扫描电子显微镜(SEM)、X射线衍射(XRD)和紫外-可见漫反射光谱(UV-Vis DRS)对薄膜的表面形貌、晶相结构、光吸收特性进行了表征,在负偏压和可见光作用下,以罗丹明B为模拟污染物对薄膜的光催化活性和稳定性进行了测定,采用电化学技术和向溶液中加入活性物种捕获剂的方法对薄膜光电催化降解机理进行了探索。结果表明:最佳工艺下制备的Ag@Ag Br/Ni膜电极是由表面沉积纳米Ag的纳米晶Ag Br颗粒构成的薄膜,具有显著的表面等离子共振效应。薄膜具有优异的光电催化活性和良好的催化稳定性,在最佳负偏压和可见光照射下反应12 min,薄膜光电催化罗丹明B(c=5 mg·L~(-1))的降解率是多孔Ti O2(P25)/ITO纳米薄膜的10.2倍。相对于未加偏压的光催化,降解率提高了2.0倍;在保持薄膜光催化活性基本不变的前提下可循环使用5次。电极表面纳米Ag粒子的等离子体共振对于光阴极反应(导带反应)的活化作用是光电催化活性提高的重要原因。提出了负偏压下Ag@Ag Br/Ni表面等离子体薄膜光电催化降解罗丹明B的反应机理。     

钛基TiO2纳米管阵列电极的光电催化性能

应用电化学阳极氧化法在纯Ti基底上制备高度有序的TiO2纳米管阵列,考察了Ti/TiO2光阳极的光电化学响应.以苯酚溶液为目标污染物,研究Ti/TiO2电极的光电催化性能,并与光催化性能进行比较.结果表明,该电极光电催化性能优于光催化性能.施加0.6 V电压时,光电催化性能最好.电化学阻抗谱分析显示,光电催化和光催化降解过程的速控步骤均为表面反应步骤,外加偏压减小了界面电荷转移阻抗,提高了光生载流子的分离效率.     

Electrochemical Monitoring of Photoelectrocatalytic Degradation of 3,4‐Dichlorophenol Using TiO2 Thin Film Modified Graphite Electrode

A novel electrode was prepared by forming TiO₂ thin films using a commercially available TiO₂ powder (Degussa P25) on graphite plates for water photoelectrocatalytic decontamination. In addition to, for the first time the photoelectrochemical degradation of 3,4‐dichlorophenol was investigated. The effects of applied potential, pH, and initial 3,4‐dichlorophenol concentration on the photoelectrocatalytic (PEC) degradation of 3,4‐dichlorophenol using ultraviolet (UV) illuminated TiO₂/graphite (TiO₂/C) thin film electrode was examined and discussed. Also, direct photolysis (DP), electrochemical oxidation (EC), photocatalytic (PC) and photoelectrocatalytic (PEC) degradation of 3,4‐dichlorophenol were compared. Results show that the best responses for PEC are obtained at applied potential 1.2 V versus reference electrode, pH 8.0 and initial 3,4‐dichlorophenol concentration 6.7 mg L^?1.     

热处理气氛对 TiO2 纳米管阵列薄膜光电催化性能的影响

 采用原位阳极氧化法在 Ti 基底上制备了高度有序的 TiO₂ 纳米管阵列薄膜, 分别在 O₂, 空气, Ar 和 H₂ 气氛中于 500 oC 进行结晶热处理, 考察了热处理气氛对 TiO₂ 纳米管阵列薄膜光电催化降解亚甲基蓝 (MB) 反应性能的影响. 结果表明, 在这些气氛中热处理得到的锐钛矿晶型的纳米管阵列薄膜对 MB 降解满足一级反应, 其速率常数分别为 4.967, 3.127, 1.989 和 1.625 h^-1 (0.5 V). 电化学阻抗分析表明, TiO₂ 纳米管的光电催化性能受控于光生电荷的传递特性. 在 O₂ 中热处理, TiO₂ 纳米管的光吸收及激发性能得以改善, 且电荷传递阻抗降低, 因而其光电催化性能最好.     

A facile one-step preparation of hierarchically-structured TiO2 nanotube array photoanodes with enhanced photocatalytic activity

Hierarchically structured TiO₂ (HST) films composed of top porous nanoparticle layer and underneath nanotube array layer are obtained by an anodization method on fluorine doped tin oxide surfaces. Compared with the TiO₂ nanotube arrays photoanode on Ti substrate, the HST photoanode exhibits a higher photoelectrocatalytic activity towards the oxidation of water and organics (e.g., glucose).     

Electrochemical monitoring of photoelectrocatalytic degradation of rhodamine B using TiO2 thin film modified graphite electrode

A commercially available TiO₂ powder (Degussa P25) has been used to prepare thin films on graphite plates. The photoelectrochemical degradation of rhodamine B was investigated using this photoelectrode. The effects of applied potential, pH, and initial rhodamine B concentration on the photoelectrocatalytic (PEC) degradation of rhodamine B using ultraviolet illuminated TiO₂/graphite (TiO₂/C) thin film electrode were examined and discussed. Also, direct photolysis, electrochemical oxidation, photocatalytic, and PEC degradation of rhodamine B were compared. Results show that the best responses for PEC are obtained at applied potential of 1.2?V vs. reference electrode, pH?4.0, and initial rhodamine B concentration of 4.2?mg?L^?1.     

Photoelectrochemical water splitting and simultaneous photoelectrocatalytic degradation of organic pollutant on highly smooth and ordered TiO2 nanotube arrays

The photoelectrochemical water splitting and simultaneous photoelectrocatalytic degradation of organic pollutant were achieved on TiO₂ nanotube electrodes with double purposes of environmental protection and renewable energy production under illumination of simulated solar light. The TiO₂ nanotube arrays (TiO₂ NTs) were fabricated by a two-step anodization method. The TiO₂ NTs prepared in two-step anodization process (2-step TiO₂ NTs) showed much better surface smoothness and tube orderliness than TiO₂ NTs prepared in one-step anodization process (1-step TiO₂ NTs). In the photoelectrochemical water splitting and simultaneous photoelectrocatalytic decomposition process, the 2-step TiO₂ NTs electrode showed both highest photo-conversion efficiency of 1.25% and effective photodecomposition efficiency with existing of methylene blue (MB) as sacrificial agent and as pollutant target. Those results implied that the highly ordered nanostructures provided direct pathway and uniform electric field distribution for effective charges transfer, as well as superior capabilities of light harvesting.     

分子印迹TiO2纳米管阵列的制备与选择性光电催化降解邻苯二甲酸二乙酯

以邻苯二甲酸二乙酯(DEP)为模板分子,在TiO2纳米管阵列(TNA)上沉积了能识别DEP分子的TiO2纳米颗粒,制备了DEP分子印迹型TNA(DM-TNA)。X射线衍射(XRD)测试表明,DM-TNA的晶体结构是锐钛矿。扫描电镜(SEM)测试显示颗粒大小约为20 nm的TiO2纳米颗粒均匀地涂覆在TNA的管壁上。光电催化降解DEP和2,4-二氯苯酚(DCP)的结果表明,DM-TNA降解DEP的活性高于非分子印迹TNA(NM-TNA),而DM-TNA降解DCP的活性低于NM-TNA。DM-TNA降解DEP的速率常数是NM-TNA的2.76倍。     

Preparation and properties of SiO2-TiO2 thin films from silicic acid and titanium tetrachloride

The preparation of SiO₂-TiO₂ thin films by the sol-gel method using silicic acid and titanium tetrachloride as starting materials was studied. The homogeneous sols were obtained by the condensation reaction of silicic acid with titanium tetrachloride in methanol-tetrahydrofuran. The dipcoating of slide glasses and silicon wafers followed by heat treatment gave oxide thin films of 88–93% transmittance, 3000–4500 Å thickness, and 1.45–1.80 refractive index, depending on heat-treatment temperature and TiO₂ content. FT-IR measurement showed that the Si-O-Ti bond is formed even in the sol and films. The variations of film thickness and refractive index on transformation from the gels into the oxides were found to be quite low.     

固态光电催化器件 ITO/TiO2/ITO 的构型和机制

 采用浸渍-提拉法将 TiO₂ 薄膜负载在具有一定电极构型的氧化铟锡 (ITO) 基底上, 制备了全固态 TiO₂ 平面型器件 (ITO/TiO₂/ITO). 采用扫描电镜对器件的表面形貌和膜厚进行了表征. 以紫外光下器件光电协同催化降解罗丹明 B(RhB) 为模型反应, 考察了器件的构型和空穴捕获剂 (乙醇) 对其光电催化性能的影响. 结果表明, 初始浓度为 10 mg/L 的 RhB 在 1.5 V 偏压和 NaCl (1.5 mol/L) 为电解质的条件下, 光照 60 min 脱色率达到 83%; 阳极面积较大的器件光电催化性能较好, 刻蚀宽度为 2 mm 时光电催化活性最高; 空穴与 TiO₂表面吸附的 H₂O 氧化生成的羟基自由基对液相光电催化降解 RhB 起着重要作用.     

Efficient photoelectrocatalytic activity of TiO2/Ti anode fabricated by metalorganic chemical vapor deposition (MOCVD)

Nanosized TiO₂/Ti photoanodes fabricated by metalorganic chemical vapor deposition (MOCVD) under different deposition temperatures were characterized and applied to the photoelectrocatalytic degradation of model pollutant of phenol. The anode prepared at 773 K was verified in anatase phase with a size about 60 nm and achieved the best photoelectrocatalytic activity, where IPCE could reach as high as 89% and the photoconversion efficiency peaked at 8.4%. The photoelectrocatalytic degradation of phenol was found well fit a pseudo-first-order kinetics, and kept stable performance in five continuous runs, confirming potential application of the electrode prepared by MOCVD for organic pollutants abatement.     

Enhancement of photoelectric catalytic activity of TiO2 film via Polyaniline hybridization

A Polyaniline (PANI)/TiO₂ film coated on titanium foil was successfully prepared using the sol-gel method followed by a facile chemisorption. Compared with pristine TiO₂, the photocatalytic (PC) and photoelectrocatalytic (PEC) degradation rates of 2,4-dichlorophenol (2,4-DCP) with the PANI/TiO₂ film were enhanced by 22.2% and 57.5%, respectively. 2,4-DCP can be mineralized more effectively in the presence of PANI/TiO₂ film. The best PEC degradation efficiency of 2,4-DCP with the PANI/TiO₂ film was acquired at an external potential of 1.5 V with a layer of 1 nm thick PANI. The PANI/TiO₂ film was characterized by Raman spectra, Fourier transform infrared spectra (FT-IR), Auger electron spectroscopy (AES), and electrochemical analysis. These results indicated that there was a chemical interaction on the interface of PANI and TiO₂. This interaction may be of significance to promote the migration efficiency of carriers and induce a synergetic effect to enhance the PC and PEC activities.     

Effect of dopant concentration on photocatalytic activity of TiO2 film doped by Mn non-uniformly

The thin films of TiO₂ doped by Mn non-uniformly were prepared by sol-gel method under process control. In our preceding study, we investigated in detail, the effect of doping mode on the photocatalytic activity of TiO₂ films showing that Mn non-uniform doping can greatly enhance the activity. In this study we looked at the effect of doping concentration on the photocatalytic activity of the TiO₂ films. In this paper, the thin films were characterized by UV-vis spectrophotometer and electrochemical workstation. The activity of the photocatalyst was also evaluated by photocatalytic degradation rate of aqueous methyl orange under UV radiation. The results illustrate that the TiO₂ thin film doped by Mn non-uniformly at the optimal dopant concentration (0.7 at %) is of the highest activity, and on the contrary, the activity of those doped uniformly is decreased. As a comparison, in 80 min, the degradation rate of methyl orange is 62 %, 12 % and 34 % for Mn non-uniform doping film (0.7 at %), the uniform doping film (0.7 at %) and pure titanium dioxide film, respectively. We have seen that, for the doping and the pure TiO₂ films, the stronger signals of open circuit potential and transient photocurrent, the better photocatalytic activity. We also discusse the effect of dopant concentration on the photocatalytic activity of the TiO₂ films in terms of effective separation of the photon-generated carriers in the semiconductor.     

Preparation of nanocrystalline porous titania films on titanium substrates by a sol–gel method with polyethylene glycol as a template

Porous nanocrystalline TiO₂ films have been prepared on cp-Ti substrates for biomedical usage by a sol–gel process from the solutions containing polyethylene glycol (PEG) as a template. Variations of the crystal structure with heat-treatment temperature determined by XRD are different for TiO₂ films and powders, due to the effect of titanium substrate. The surface texture of porous TiO₂ films is analyzed by means of SEM and found to greatly depend on the concentration and molecular weight of PEG. The pore formation mechanism is discussed in relation to the self-assembly of PEG and phase separation between PEG adsorbed on TiO₂ oligomers and ethanol.     

Stress and Cracks in Gel-Derived Ceramic Coatings and Thick Film Formation

Residual stress was evaluated by measuring the substrate curvature for alkoxide-derived silica and titania films deposited on silica glass substrates. The residual stress was tensile, increasing with increasing heat-treatment temperature. The stress in fired films was affected greatly by water/alkoxide ratio and chelating agents in starting solutions. Secondly, in situ observation was made on cracking of gel films subjected to heat-treatment. Silica and titania gel films deposited on silicon wafers were cracked in the heating-up stage at temperatures of 100°–400°C, depending on the film thickness and heating rate. Larger thickness and lower heating rates were found to lower the cracking onset temperature. Finally, organic polymers with amide groups were demonstrated to increase the uncracking critical thickness. The polymers include polyvinylpyrrolidone and polyvinylacetamide, allowing single layer ceramic coating films over 1 m in thickness to be formed without cracking.     

钨掺杂BiVO4光阳极降解环丙沙星的表面态行为

采用简单浸渍的方法对BiVO₄光阳极进行表面钨(W)掺杂,以环丙沙星(CIP)为药品和个人护理产品(PPCPs)模型污染物,研究了W掺杂BiVO₄光阳极降解CIP的表面态行为。结果表明,低浓度W掺杂对BiVO₄光阳极的晶体结构、表面形貌和光吸收性能没有显著影响。但W掺杂取代了BiVO₄光阳极表面的V⁵⁺,能抑制BiVO₄光阳极表面V⁵⁺/V⁴⁺还原过程,减少复合中心表面态,同时引入更多氧空穴,增加活性位点表面态。CIP的降解反应受表面活性位点控制。表面W掺杂能有效促进CIP降解的电荷转移,提高BiVO₄光阳极光电催化降解性能。     

钨掺杂BiVO4光阳极降解环丙沙星的表面态行为

采用简单浸渍的方法对BiVO₄光阳极进行表面钨(W)掺杂,以环丙沙星(CIP)为药品和个人护理产品(PPCPs)模型污染物,研究了W掺杂BiVO₄光阳极降解CIP的表面态行为。结果表明,低浓度W掺杂对BiVO₄光阳极的晶体结构、表面形貌和光吸收性能没有显著影响。但W掺杂取代了BiVO₄光阳极表面的V⁵⁺,能抑制BiVO₄光阳极表面V⁵⁺/V⁴⁺还原过程,减少复合中心表面态,同时引入更多氧空穴,增加活性位点表面态。CIP的降解反应受表面活性位点控制。表面W掺杂能有效促进CIP降解的电荷转移,提高BiVO₄光阳极光电催化降解性能。     

Photoelectrochemical oxidation behavior of organic substances on TiO2 thin-film electrodes

The photoelectrocatalytic oxidation characteristics of salicylic acid, formic acid and methanol on anodized nanoporous titanium dioxide (TiO₂) thin-films were investigated by using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. From dark to ultraviolet illumination, the open circuit potential (OCP) and film resistance of TiO₂ films decreased markedly. A general equivalent circuit model was proposed for the photoelectrochemical system anodic TiO₂ thin-film electrode/test solution. The photoelectrochemical oxidation process of the organic compounds showed similar impedance features at OCP and was controlled by the charge transfer step. According to the polarization curves of the base solution and organic solutions, the kinetic rate curves for the photoelectrocatalytic oxidation of pure organic species were obtained as a function of the potential bias. One photooxidation peak was first observed at a bias potential of ca. 0.26 V for these species with low concentrations.