可见光响应超亲水TiO2薄膜研究进展

介绍了TiO2薄膜的超亲水机理,论述了实现TiO2薄膜可见光响应超亲水性的改性技术,主要包括构建粗糙结构薄膜、贵金属沉积、离子掺杂、表面光敏化、半导体复合、TiO2/SiO2复合、多种改性方法联合使用等方法。总结了目前超亲水TiO2薄膜主要存在制备工艺复杂、改性条件苛刻、亲水寿命短等问题,并指出采用溶胶-凝胶法,利用多种改性方法的联合使用是解决这些问题的重要研究方向。     

Ag掺杂Ti/PbO2电极的制备及其在苯酚降解中的应用

使用化学还原和电沉积的方法制备了单质银（Ag）掺杂的Ti/PbO₂电极（Ti/Ag-PbO₂）。在保持镀银液浓度一定的条件下,通过改变镀银的时长制备出三种银含量的钛基体二氧化铅电极（Ti/Ag1-PbO₂、Ti/Ag2-PbO₂、Ti/Ag3-PbO₂）。利用X射线光电子能谱（XPS）和X射线荧光光谱分析（XRF）确定了PbO₂电极中Ag的价态和掺杂量。扫描电子显微镜（SEM）和X射线衍射（XRD）结果表明,Ag掺杂未明显改变电极的表面形态和晶型。根据涂层附着力测试试验发现,掺银PbO₂电极与基底之间有更好的结合力,电极使用寿命提高了约2.5倍。电化学交流阻抗谱（EIS）和循环伏安法（CV）测试结果表明,Ag的掺杂大幅降低了PbO₂电极的电荷转移电阻,提高了电极的电催化活性。利用掺银量2.7%（质量分数）的Ti/PbO₂电极降解100mg/L的苯酚水溶液,相较常规Ti/PbO₂电极,完全降解时间缩短了33.3%,降解能耗下降了34%。     

超亲水微纳复合结构表面热沉强化润湿与传热实验

利用碱辅助的表面氧化法在紫铜微槽群热沉表面生成了氢氧化铜纳米棒阵列结构,制备出一种全新的超亲水微纳复合结构表面热沉。并以蒸馏水为液体工质,进行了纯蒸发条件下微槽群热沉、微纳复合结构表面热沉和超亲水微纳复合结构表面热沉的润湿及传热特性的对比实验研究。实验结果表明：氢氧化铜纳米棒阵列结构使得原始亲水表面的亲水性更好,随着表面纳米棒数量的不断增多,接触角不断减小,最低为9.5°,可以进一步形成超亲水微纳复合结构表面。与无纳米结构的微槽群热沉相比,在相同输入加热功率下,微纳复合槽群热沉具有更高的液体润湿高度和更好的传热性能,而超亲水微纳复合结构表面热沉的形成会进一步提高强化润湿和传热效果,相比于紫铜微槽群热沉,超亲水微纳复合结构表面热沉内液体的润湿高度提高了300%,表面温度降低了15℃左右。     

可见光照射下Fe3+掺杂量对玻璃基TiO2薄膜亲水性能的影响

采用溶胶-凝胶法在普通玻璃衬底上制备了不同Fe3+掺杂量的TiO2薄膜.通过X射线光电子能谱仪(XPS)、X射线衍射仪(XRD)、场发射扫描电子显微镜(SEM)、UV-Vis-NIR3600型紫外-可见分光光度计、CA-XP150型水接触角测试仪研究了不同Fe3+掺杂量对TiO2薄膜微观结构、表面形貌、光学性能和亲水性能的影响.结果 表明,所制备的不同Fe3+掺杂量的TiO2薄膜均具有锐钛矿结构;随着Fe3+掺杂量的增大,薄膜样品(镀膜玻璃)在可见光区的平均透过率从70.28％降低到61.45％.当薄膜中Fe3+掺杂量为0.25mol％时,薄膜样品具有最佳的亲水性能,在可见光照射120 min后水接触角降到3.2°;在黑暗中放置20 h后水接触角恢复到4.0°.     

稀土Eu3+掺杂对SnO2薄膜光学和电学性质的影响

基于旋涂法制备了Eu³⁺掺杂的SnO₂薄膜，并通过紫外-可见分光光度计(UV-Vis)、电流-电压测试和原子力显微镜(AFM)等对样品的光学性质、电学性质和表面形貌进行了表征。研究发现，在200nm～380nm的波长范围内，掺杂15at%Eu³⁺的SnO₂薄膜光吸收率最高；在380nm～700nm的可见光范围内，掺杂15at%Eu³⁺的SnO₂薄膜光透射率较强，掺杂20at%Eu³⁺的SnO₂薄膜光吸收率最强。随着Eu³⁺掺杂浓度的增加，SnO₂薄膜的电阻增加，表面的平均粗糙度显著降低。     

碳掺杂ZnO薄膜及可见光催化氮合成氨

采用磁控溅射双靶共溅射方法，在玻璃表面成功制备了高催化活性的碳掺杂ZnO薄膜。通过X射线衍射仪、高倍透射电镜、X射线光电子能谱仪等表征了碳掺杂ZnO薄膜，并在可见光催化氮合成氨实验中评价了薄膜的催化剂性能。结果表明碳掺杂的ZnO薄膜中存在碳量子点，尺寸为4nm，晶面间距0.21nm，薄膜可以吸收可见光。同时ZnO晶格中的碳提高了ZnO导带的位置，增强了激发电子的还原能力。当碳掺杂量为1.03%时，氨氮产量为5.15×10^–4mol/(h·cm²)。利用反胶束蚀刻法又成功地在玻璃表面蚀刻出了微米坑，坑口径为0.5～2μm，坑深为100～500nm。与平面玻璃表面上的薄膜比较，在光催化氮合成氨实验中微米坑玻璃表面上薄膜的氨氮产量提高了约1.4倍，膜基结合力提高了2倍多。结合薄膜的能带结构图讨论了碳掺杂ZnO薄膜的光催化机理。     

表面改性对掺杂TiO_2纳米薄膜亲水性的影响

文章采用溶胶-凝胶法制备La3+掺杂纳米TiO2薄膜,实验探讨了硝酸溶液表面改性对掺杂纳米TiO2薄膜亲水性的影响。采用X射线衍射分析不同掺杂浓度纳米TiO2的物相,分别利用扫描电镜与接触角测量仪观察TiO2薄膜表面形貌及其亲水性能。实验表明:经0.1mol/L的硝酸溶液中改性后的La3+掺杂纳米TiO2薄膜具有超亲水性。     

硼氮共掺杂TiO2粉末制备及光催化活性研究

采用溶胶-凝胶法制备硼氮共掺杂TiO₂光催化剂,利用X射线衍射、X射线光电子能谱及紫外-可见光漫反射光谱手段对制备的催化剂进行表征。结果表明,硼和氮均以间隙方式进入TiO₂晶格中,形成Ti-O-B、Ti-O-N和Ti-O-B-N结构,提高了催化剂活性;B-N-TiO₂吸收带边明显红移,表明催化剂对可见光吸收增强。可见光降解甲基橙结果表明,B-N-TiO₂的活性明显高于B-TiO₂和N-TiO₂,说明硼氮共掺杂改性对提高TiO₂可见光活性具有协同作用。     

电化学Fe掺杂增强FTO薄膜的可见光光电化学性能

通过在Fe SO4溶液中将FTO(F掺杂SnO_2)导电玻璃电化学阴极极化,随后在500°C空气中热氧化,制备出对可见光有响应的Fe掺杂FTO薄膜。用扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)表征了薄膜的形貌、结构和表面特性。在可见光下测试了薄膜在1.0 mol/L NaOH溶液中零偏压下的光电流-时间曲线。结果显示,电化学修饰后的FTO薄膜表面呈纳米多孔形貌,薄膜中有1%(原子分数)左右的Fe元素掺杂且存在正交结构SnO_2和四方结构SnO_2两种物相。Fe掺杂FTO的光电流密度为0.5μA/cm~2,比无Fe掺杂的FTO薄膜(0.019μA/cm~2)显著增强。     

TiO2/SiO2复合薄膜的制备及其自清洁性能

利用热陈化法得到的纳米TiO2粒子及SiO2聚合物胶粒通过浸渍-提拉技术制备了具有自清洁功能的TiO2/SiO2复合薄膜。考察了SiO2的复合比例对薄膜的表面形貌、透光率、光致亲水及自清洁性能的影响。随着SiO2复合体积分数的增大,薄膜的表面粗糙度、可见光透过率、光致亲水及自清洁性能显示了相似的变化规律。即在V(SiO2)=25%左右时,薄膜的各项特性或性能达到最大值或最小值。该薄膜在室外放置28天后,仍能显示超亲水性能。     

Preparation and electrochemical properties of composites of carbon nanotubes loaded with Ag and TiO2 nanoparticle for use as anode material in lithium-ion batteries

Carbon nanotubes (CNTs) loaded with Ag and TiO₂ nanoparticles (Ag-TiO₂/CNTs) are a composite showing promise as an anode material in lithium-ion batteries. Here we prepare Ag-TiO₂/CNTs via hydrolysis and reduction processes. The morphology, structure, and electrochemical performance of the composite were investigated by transmission electron microscopy, X-ray diffraction, and a variety of electrochemical techniques. The results show that the TiO₂ and Ag nanoparticles were uniformly deposited on the surface of CNTs with crystallite sizes of ∼12 and 30 nm, respectively. The Ag-TiO₂/CNTs anode materials showed superior cycling stability and a high reversible capacity of 172 mAh/g after 30 cycles. Ag addition not only increases the electronic conductivity of the composites, but also allows convenient transfer of Li-ion in the composite structure.     

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.     

Enhanced photoresponse and photocatalytic activities of graphene quantum dots sensitized Ag/TiO2 thin film

TiO₂ thin films were fabricated through hydrothermal method. Silver nanoparticles were loaded on TiO₂ thin films via photoreduction technique. Subsequently, the graphene quantum dots (GQDs) were spin‐coated on the Ag/TiO₂ nanocomposites thin films. The crystal structure, surface morphology and UV‐vis absorbance were tested by XRD, SEM and ultraviolet‐visible spectrophotometer. These results indicated that Ag nanoparticles and GQDs are anchored on the TiO₂ nanorods. Absorbance of Ag/TiO₂ and GQDs/Ag/TiO₂ nanocomposite thin films have been extended into the visible region. Visible‐light response of the samples were investigated by electrochemical workstation. The photoresponse of the sample can be enhanced by sensitization of the Ag nanoparticles and GQDs. The enhanced visible‐light response may be due to the surface plasmon resonance of silver nanoparticles and visible absorbance of GQDs. The highest photocatalytic activity has been observed in the 9‐GQDs/Ag/TiO₂ composite thin film. The efficient charge separation and transportation can be achieved by introducing the Ag nanoparticles and GQDs in the TiO₂ thin film.     

Simultaneous Laser‐Induced Reduction and Nitrogen Doping of Graphene Oxide in Titanium Oxide/Graphene Oxide Composites

Titanium oxide/graphene oxide nanocomposite thin films were grown by ultraviolet (UV) matrix‐assisted pulsed laser evaporation (MAPLE) technique in controlled oxygen or nitrogen atmospheres. The effect of graphene oxide addition and laser‐induced reduction as well as nitrogen doping on the wetting behavior and photoactive properties of titanium oxide thin films was investigated. Hydrophobic to hydrophilic conversion of titanium oxide films takes place progressively as the relative amount of graphene oxide in the MAPLE composite target increases. Nitrogen doping leads to further decrease of the static contact angle of the composite films. The photoactive properties of the synthesized materials were investigated through the evolution of contact angle under UV light irradiation. Wetting properties of both TiO₂ and TiO₂/GO nanocomposite thin films improved upon exposure to UV light.     

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.     

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.     

Hydrothermal preparation of Ag-TiO2 nanostructures with exposed {001}/{101} facets for enhancing visible light photocatalytic activity

Nano-composite materials of Ag nanoparticles dispersed TiO₂ nanocubes with exposed {001}/{101} crystal faces were fabricated mainly via a flexible one-step method of hydrothermal treatment with different content of Ag from 1 up to 3 mol%. Prepared photocatalysts were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscopy, UV–vis absorption spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. These analysis was carried out for understanding the contribution of different content of silver for enhancing the photocatalytic activity of TiO₂ nanocubes. Prepared silver nanoparticles had small particle size and grafted to the {101} crystal face of TiO₂ with the role of template control agent and linking agent. The photocatalytic performance of Ag-TiO₂ nanocubes were researched via Rhodamine B dye removal under visible light irradiation ( ≧420 nm). Ag-TiO₂ composite materials with the content of 2 mol% Ag showed the best photocatalytic activity for degradation of Rhodamine B, which was five times more than bare TiO₂ and associated with the localized surface plasmon resonance (LSPR) propelled effect. The mechanism by which silver enhanced the photocatalytic activity of TiO₂ was also demonstrated.     

Photocatalytic Water Splitting on Visible Light-responsive TiO2 Thin Films Prepared by a RF Magnetron Sputtering Deposition Method

The development of visible light-responsive TiO₂ (Vis-TiO₂) thin films has been achieved by applying a radio-frequency magnetron sputtering deposition (RF-MS) method. Pt-loaded Vis-TiO₂ thin films act as photocatalysts to decompose water involving sacrificial reagent such as methanol or silver nitrate even under visible light (λ ≧ 420 nm) irradiation. It was also found that Pt-loaded Vis-TiO₂ thin films decompose pure water into H₂ and O₂ stoichiometrically under light irradiation of wavelengths longer than 390 nm. Vis-TiO₂ thin films exhibit columnar structures perpendicular to the substrate and a declined composition of the O/Ti ratio from the surface (O/Ti = 2.00) to bottom (O/Ti = 1.93). This unique structure (anisotropic structure) of Vis-TiO₂ can be considered an important factor in the modification of the electronic properties of Vis-TiO₂ thin films, enabling the absorption of visible light. Furthermore, the effect of the Pt loadings on the photocatalytic activity of the TiO₂ thin films was investigated and the optimum Pt loading was determined to be 21 μ g/cm² as Pt metal     

Simultaneous improvement of photocatalytic and superhydrophilicity properties of nano TiO2 thin films

Anatase TiO₂ nano thin films were prepared on glass substrates by sol–gel dip coating method using Tween-80 as a surfactant, TiCl₄ as the Ti precursor, and ethanol as a solvent. Atomic force microscopy, X-ray diffraction, and UV–Vis. photospectrometery experiments were performed to analyze the surface, structural and optical characteristics of the films. The effects of chemical aging time on the morphology, photocatalytic and superhydrophilicity behaviors of the films were studied. We show there is an optimum aging time at 2 h which photocatalytic and superhydrophilicity properties are at their maximum values simultaneously. This is useful in the self-cleaning industry.     

Surfactant-catalyzed SiO2 thin films preparation and characterization

SiO₂ thin films are in high demand for wide range of applications including microelectronics, optoelectronics, solar energy conversion, photocatalysis, and self-cleaning coatings. The performance of thin film is strongly influenced by surface properties like surface roughness, thickness, morphology, wetting behavior, and thermal stability. In these applications, the SiO₂ sols were prepared using tetraethylorthosilicate as a source of SiO₂ and deposited on 100?×?40?×?2?mm³ glass slide using dip-coating method for 2?min and calcined at 250?°C for 30?min. The SiO₂ thin films were obtained using DTAB, SDS, and Tween 20 (Tw 20) surfactants with the thickness of 36.92, 47.15, and 52.39?nm, respectively. Surface morphology was studied with AFM and surface roughness was depicted with 0.9528, 3.6534, and 0.9294?nm. Contact angle measurements have been performed with goniometer to evaluate the wetting behavior of the film. The contact angle of 58.01°, 48.40°, and 37.88° was observed with SDS, DTAB, and Tw 20 film, respectively. The SiO₂ thin films with SDS showed more surface roughness and water repelling ability when compared to DTAB and least with Tw 20.