硫掺杂TiO2/Ti光电极制备及其可见光光电催化性能

为了提高TiO2/Ti光电极在可见光下的光电催化活性,采用阳极氧化法制备了一种新型的硫掺杂TiO2/Ti光电极.采用扫描电子显微镜、X射线衍射、X射线荧光光谱等技术对光电极进行了表面形貌、结晶形态、晶粒尺寸、硫的掺杂量和价态以及吸光性能表征.研究表明:硫掺杂TiO2/Ti光电极的最佳制备条件为:成膜电压160V、电流密度100mA/cm2、Na2SO3质量浓度750mg/L;所制备的光电极具有良好的光电催化氧化降解邻苯二甲酸二甲酯活性,并能有效地矿化其中间产物;与TiO2/Ti电极相比,硫的掺杂可以显著提高其在可见光下的光电催化性能.     

Preparation N-F-codoped TiO2 nanorod array by liquid phase deposition as visible light photocatalyst

An efficient method for the preparation of N-F-codoped visible light active TiO₂ nanorod arrays is reported. In the process, simultaneous nitrogen and fluorine doped TiO₂ nanorod arrays on the glass substrates were achieved by liquid phase deposition method using ZnO nanorod arrays as templates with different calcination temperature. The as-prepared samples were characterized by Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectra measurements. It was found that calcination temperature is an important factor influencing the microstructure and the amount of N and F in TiO₂ nanorod arrays samples. The visible light photocatalytic properties were investigated using methylene blue (MB) dye as a model system. The results showed that N-F-codoped TiO₂ nanorod arrays sample calcined at 450 °C demonstrated the best visible light activity in all samples, much higher than that of TiO₂ nanoparticles and P25 particles films.     

Visible light photoelectrocatalysis with salicylic acid-modified TiO2 nanotube array electrode for p-nitrophenol degradation

This research focused on immersion method synthesis of visible light active salicylic acid (SA)-modified TiO₂ nanotube array electrode and its photoelectrocatalytic (PEC) activity. The SA-modified TiO₂ nanotube array electrode was synthesized by immersing in SA solution with an anodized TiO₂ nanotube array electrode. Scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), UV–vis diffuse reflectance spectrum (DRS), and Surface photovoltage (SPV) were used to characterize this electrode. It was found that SA-modified TiO₂ nanotube array electrode absorbed well into visible region and exhibited enhanced visible light PEC activity on the degradation of p-nitrophenol (PNP). The degradation efficiencies increased from 63 to 100% under UV light, and 79–100% under visible light (λ > 400 nm), compared with TiO₂ nanotube array electrode. The enhanced PEC activity of SA-modified TiO₂ nanotube array electrode was attributed to the amount of surface hydroxyl groups introduced by SA-modification and the extension of absorption wavelength range.     

Preparation of Fe-doped TiO2 nanotube arrays and their photocatalytic activities under visible light

Fe-doped TiO₂ nanotube arrays have been prepared by the template-based liquid phase deposition method. Their morphologies, structures and optical properties were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and UV-vis absorption spectroscopy. Their photocatalytic activities were evaluated by the degradation of methylene blue under visible light. The UV-vis absorption spectra of the Fe-doped TiO₂ nanotube arrays showed a red shift and an enhancement of the absorption in the visible region compared to the undoped sample. The Fe-doped TiO₂ nanotube arrays exhibited good photocatalytic activities under visible light irradiation, and the optimum dopant amount was found to be 5.9 at% in our experiments.     

Mn-doped TiO2 nanopowders with remarkable visible light photocatalytic activity

TiO₂ nanocrystalline powders with various Mn-doping levels were synthesized by the sol-gel process using tetrabutyl titanate and manganese nitrate as precursors. The crystal structure, morphology, doping concentration, optical absorption property, and elemental state of the obtained samples were analyzed. TEM results showed that the synthesized TiO₂ powders were anatase nanoparticles about 7 nm in size. EDX and XPS analyses proved the incorporation of Mn ions into the TiO₂ lattice. A remarkable red shift of the absorption edge was achievable by increased Mn content, leading to gigantically narrowed energy gap to permit absorption well into the infrared spectral region. The dramatic optical absorbance of the doped TiO₂ nanopowders in the visible spectral region led to strong photocatalytic activity under visible light illumination, which was observed by measuring the degradation of methylene blue. In contrast, little degradation was observed for the pure TiO₂ powder. The optimum Mn/Ti ratio was observed to be 0.2 at.% for photocatalytic applications.     

Fabrication of TiO2/Au nanorod arrays employing a positive sacrificial ZnO template and their electrochromic property

A novel method to fabricate large scale TiO₂/Au nanorod array using a positive sacrificial ZnO template has been developed. This method includes a two-step process, (1) preparation of ZnO/Au nanorod array by a simple low-temperature hydrothermal process, and (2) preparation of TiO₂/Au nanorod array by electrochemically induced sol-gel process. The TiO₂/Au nanorod array has showed a reversible electrochromism in lithium-ion-containing organic electrolyte. The coloration and bleaching throughout a visible range can be switched on and off within a few seconds.     

Hydrothermal synthesis and characterization of TiO2 nanorod arrays on glass substrates

Large-scale, well-aligned single crystalline TiO₂ nanorod arrays were prepared on the pre-treated glass substrate by a hydrothermal approach. The as-prepared TiO₂ nanorod arrays were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. X-ray diffraction results show that the main phase of TiO₂ is rutile. Scanning electron microscopy and transmission electron microscopy results demonstrate that the large-scale TiO₂ nanorod arrays grown on the pre-treated glass substrate are well-aligned single crystal and grow along [0 0 1] direction. The average diameter and length of the nanorods are approximately 21 and 400 nm, respectively. The photocatalytic activity of TiO₂ nanorod arrays was investigated by measuring the photodegradation rate of methyl blue aqueous solution under UV irradiation (254 nm). And the results indicate that TiO₂ nanorod arrays exhibit relatively higher photocatalytic activity.     

Hydrophilicity on carbon-doped TiO2 thin films under visible light

Carbon-doped TiO₂ thin films in the anatase phase with dopant concentrations of 1.1, 0.9, and 0.7 mol% were fabricated by a radio-frequency magnetron sputtering method. Dopant carbons were located at the oxygen sites. Carbon substitution caused the absorbance edge and/or the shoulder of TiO₂ to shift to a higher wavelength region. Carbon-doped TiO₂ thin films underwent a hydrophilic conversion when irradiating with visible light (400–530 nm). The hydrophilic property under visible light was inferior to that under ultraviolet light, which is explained by considering that the visible light sensitivity originates from the localized C 2p formed in the band-gap.     

Enhanced photoelectrocatalytic activity in TiO2 nanotube arrays modified with TiO2 nanoparticles

The use of TiO₂ nanotube arrays fabricated by anode oxidation of titanium sheets as a photoelectrocatalyst is limited by low surface activity owing to passive crystallization post-treatment. We report here on a vacuum assisted filling route for modifying TiO₂ nanotube arrays using high-activity anatase TiO₂ nanoparticles as a filling. Photoelectrocatalytic degradation experiments show that a nearly 4-fold activity enhancement in photoelectrocatalysis is achieved and good photoelectrocatalytic stability is kept after the nanotube arrays are filled with the high-activity TiO₂ nanoparticles. The remarkable enhancement in photoelectrocatalysis is ascribed to the key modification of the TiO₂ nanotube arrays using the high-activity TiO₂ nanoparticles. Our findings provide an insight into designing excellent photoelectrocatalysts by filling TNAs with available high-activity TiO₂ nanoparticles.     

Rutile TiO2 nanorod arrays directly grown on Ti foil substrates towards lithium-ion micro-batteries

Nanosized rutile TiO₂ is one of the most promising candidates for anode material in lithium-ion micro-batteries owing to their smaller dimension in ab-plane resulting in an enhanced performance for area capacity. However, few reports have yet emerged up to date of rutile TiO₂ nanorod arrays growing along c-axis for Li-ion battery electrode application. In this study, single-crystalline rutile TiO₂ nanorod arrays growing directly on Ti foil substrates have been fabricated using a template-free method. These nanorods can significantly improve the electrochemical performance of rutile TiO₂ in Li-ion batteries. The capacity increase is about 10 times in comparison with rutile TiO₂ compact layer.     

TiO2 coated SnO2 nanosheet films for dye-sensitized solar cells

TiO₂-coated SnO₂ nanosheet (TiO₂-SnO₂ NS) films about 300 nm in thickness were fabricated on fluorine-doped tin oxide glass by a two-step process with facile solution-grown approach and subsequent hydrolysis of TiCl₄ aqueous solution. The as-prepared TiO₂-SnO₂ NSs were characterized by scanning electron microscopy and X-ray diffraction. The performances of the dye-sensitized solar cells (DSCs) with TiO₂-SnO₂ NSs were analyzed by current-voltage measurements and electrochemical impedance spectroscopy. Experimental results show that the introduction of TiO₂-SnO₂ NSs can provide an efficient electron transition channel along the SnO₂ nanosheets, increase the short current density, and finally improve the conversion efficiency for the DSCs from 4.52 to 5.71%.     

Fabrication of TiO2 nanotube film by well-aligned ZnO nanorod array film and sol-gel process

High density TiO₂ nanotube film with hexagonal shape and narrow size distribution was fabricated by templating ZnO nanorod array film and sol-gel process. Well-aligned ZnO nanorod array films obtained by aqueous solution method were used as template to synthesize ZnO/TiO₂ core-shell structure through sol-gel process. Subsequently, TiO₂ nanotube array films survived by removing the ZnO nanorod cores using wet-chemical etching. Polycrystalline anatase TiO₂ nanotube films were ∼ 1.5 μm long and ∼ 100 nm in inter diameter with a wall thickness of ∼ 10 nm.     

Low-temperature hydrothermal synthesis of flower-like ZnO microstructure and nanorod array on nanoporous TiO2 film

A novel ZnO architecture, with flower-like microstructure on the top layer and nanorod arrays on the bottom layer, was hydrothermally synthesized on the Fluorine-doped SnO₂ (FTO) conducting glass pre-coated with nanoporous TiO₂ film. The as-prepared architecture was characterized with Field-emission scanning electron microscopy (FE-SEM) and X-ray diffractometer (XRD). Dye-sensitized solar cell studies showed that the power conversion efficiency (η) was 1.26% for this novel ZnO architecture-covered TiO₂ electrode.     

PANI/TiO2复合材料的合成条件研究及可见光催化性能

采用原位化学氧化聚合法制备了一系列不同酸掺杂和不同氧化剂用量的PANI/TiO2复合光催化材料,利用IR对其结构进行表征,并研究了该系列光催化材料在可见光下对甲基红的降解情况.通过研究表明当苯胺与TiO2的质量比为5∶1,AN与APS摩尔比为2∶1时,可见光催化活性较好;硫酸掺杂的PANI/TiO2可见光催化活性较好.     

Photocatalytic activity of nitrogen doped rutile TiO2 nanoparticles under visible light irradiation

This work provides the design and synthesis of nitrogen doped rutile TiO₂ nanoparticles working as efficient photocatalysts under visible light irradiation. Nitrogen doped rutile TiO₂ nanoparticles are synthesized through the surface nitridation of rutile nanoparticles, which have been prepared in advance. The experimental results show that the nitrogen element is easily doped into the lattice of TiO₂ nanoparticles and its doping amount increases with the decrease of nanocrystallite size. The photocatalytic activity of the nanoparticles under visible light irradiation is correlated not only with the amount of doped nitrogen element but also with the morphology and crystallinity of nanoparticles.     

Synthesis of size-tunable ZnO nanorod arrays from NH3·H2O/ZnNO3 solutions

Well-aligned crystalline ZnO nanorod arrays were fabricated via an aqueous solution route with zinc nitrate and ammonia as precursors. Dip-coating was firstly utilized to form a ZnO film on ITO substrate as a seed layer for subsequent growth of ZnO nanorods. The effects of NH₃·H₂O/ZnNO₃ molar ratio, ZnNO₃ concentration, growth temperature and time on nanorod morphology were respectively investigated. It was found that the size of nanorod is mainly determined by the molar ratio and concentration. XRD demonstrates that ZnO nanorods are wurtzite crystal structures preferentially orienting in the direction of the c-axis. SEM confirms that ZnO nanorods grew up perpendicular to the substrate. The diameter and length were tunable in a broad range from 80 nm to 500 nm and 250 nm up to 8 μm, respectively. The aspect ratio changed from 3 to 17 mainly dependent on composition of the aqueous solution.     

Fabrication of nitrogen-doped mesoporous TiO2 layer with higher visible photocatalytic activity by plasma-based ion implantation

Nitrogen-doped porous TiO₂ layers were fabricated on the titanium substrate by plasma-based ion implantation sequentially using He, O₂ or N₂ atmospheres. Post implantation annealing at 570 °C generates a mixture of anatase with a small fraction of rutile in the implanted layer. In order to enlarge the specific surface area, a mesoporous surface structure was produced by exposing the helium bubbles at the sub-surface after removing the surface compact layer using argon ion sputtering. Nitrogen doping extends the photoresponse into the visible light region. Moreover, a lower dose of 4 × 10¹⁵ N/cm² induces a stronger visible light absorption. The photodegradation of Rhodamine B solution with visible light sources indicates that the mesopores at the fresh surfaces and nitrogen doping, both individually and in combination, contribute to an apparent increase in the photodegradation rate.     

Investigation into real-time pressure sensing properties of SnO2, TiO2, and TiO2/ZnO thick films with interdigitated electrodes

The pressure sensing properties of nanocomposite SnO₂, TiO₂, and TiO₂/ZnO thick film capacitors with interdigitated electrodes are investigated. To form the dielectric layers, the metal oxides powders were respectively mixed with isopropanol, wet ball milled for 24 h, then the mixtures were dried at 120 °C and further the powders were placed under 2 tonnes of pressure to form pellets, which were fired at 1250 °C (rate of 5 °C/min) in a vacuum of 6 × 10⁻³ mbar for 5 h, followed by cooling (rate of 3 °C/min). After firing, the resultant nanopowders were mixed with 7 wt.% of polyvinyl butyral (binder) and suitable amount of ethylenglycolmonobutylether (solvent) to form the pastes. These were screen-printed over the Ag electrodes on alumina substrates to form SnO₂, TiO₂, and TiO₂/ZnO capacitor pressure sensors accordingly. The evaluation of pressure sensing properties of these sensors was performed using a HP 4192A Impedance Analyser, which recorded the changes in the values of the capacitances under different mechanical stresses. At the applied load of 5 kPa, the response times of 2.5 s, 5.6 s and 4 s were recorded for SnO₂, TiO₂, and TiO₂/ZnO sensors, respectively. In addition to instant response times, these pressure sensors have the advantage of being reusable, as their electrical properties were restored to the original value after annealing for 2 h at 80 °C. Moreover, one year later after the initial testing, the sensors were still operational and produced similar time responses to pressure.     

ZnO nanorod arrays for photoelectrochemical cells

The splitting of water using photoelectrochemical (PEC) cells to produce hydrogen is one of the most sustainable forms of energy production and more and more 1-D nanostructrues semiconductors used as photoelectrodes have been studied extensively. However, it is not clear whether the photoconversion efficiencies of such nanostructure devices are limited by the architectures of the 1-D electrodes. Here, we explore the effect of the architecture like the length and width of ZnO nanorods on the PEC cells performance for the first time. The as-prepared nanorods have diameters of 40-50 nm and lengths of 400-800 nm. Preliminary measurements exhibit that the resulting electrodes have promising PEC properties. Mott-Schottky measurements give a flat-band potential of +0.10 V, a carrier density of 3.7 x 10(17) cm(-3), and a space-charge layer of 26 nm. The photocurrent of 800 nm-long nanorods shows 10 times higher than that of 400 nm-long ones, and an encouraging maximum photoconversion efficiency of 0.25% is obtained under illumination of 100 mW/cm2 (AM 1.5), which is among the highest reported for an undoped ZnO photoelectrode to date.     

Photocatalytic reduction of methylene blue by TiO2 nanotube arrays: effects of TiO2 crystalline phase

TiO₂ nanotube arrays were synthesized by anodization of Ti metal sheets followed by thermal annealing at elevated temperatures from 400 to 600 °C. Scanning electron microscopic measurements showed that dense arrays of nanotubes were produced with the inner diameter about 100 nm, wall thickness 35 nm, and length about 10 μm. X-ray diffraction measurements showed that the as-prepared nanotubes were largely amorphous, whereas thermal annealing led to the formation of well-defined anatase crystalline phase. More interestingly, at 470 °C, the brookite crystalline phase also started to emerge, which became better defined at 500 °C and disappeared eventually at higher temperatures, a phenomenon that has not been observed previously in TiO₂ nanotube arrays prepared by anodization. The impacts of the TiO₂ nanocrystalline structure on the photocatalytic activity were then examined by using the reduction of methylene blue in water as an illustrating example. Upon exposure to UV lights, the visible absorption profiles of methylene blue exhibited apparent diminishment. Based on these spectrophotometric measurements, the corresponding pseudo-first-order rate constant was estimated, and the sample thermally annealed at 500 °C was found to exhibit the highest activity. The strong correlation between the TiO₂ crystalline characteristics and photocatalytic performance suggests that the synergistic coupling of the anatase and brookite crystalline domains led to effective charge separation upon photoirradiation and hence improved photocatalytic activity, most probably as a consequence of the vectorial displacement at the nanoscale junctions between these crystalline grains that impeded the dynamics of electron–hole recombination. These results demonstrate the significance of nanoscale engineering in the manipulation of oxide photocatalytic performance.