Fabrication and self-cleaning properties of reduced graphene oxide/TiO2:Nd nanohybrid thin films

Self-cleaning is an important technique for environmental purification. In this work, a series of reduced graphene oxide (rGO)-TiO₂:Nd nanohybrid films were deposited and characterized by various analysis techniques. The rGO incorporation and Nd doping obviously enhanced the self-cleaning properties including photocatalytic activity, photo-induced superhydrophilicity, and conductivity of the TiO₂ film. The effect of Nd content and rGO proportion on the self-cleaning properties was also studied. The efficient synergistic effect of rGO and Nd on the self-cleaning properties was observed and mainly ascribed to interface-induced effect. The measurement of band energy level and optical conductivity confirmed the interface-induced effect.     

二氧化钛光催化自清洁材料研究进展

自清洁材料可将表面附着的污染物在自然外力和外界能力的作用下,将材料表面的污染物去除.TiO2是一种半导体金属氧化物,且具有TiO2独特的光诱导超亲水性质以及光催化降解有机物的特性,是一种理想的光催化自清洁材料.介绍了基于TiO2的自清洁材料,包括TiO2光诱导自清洁、TiO2光催化自清洁和TiO2复合光催化材料并进行了...     

Influence of physico-structural properties on the photocatalytic activity of sol-gel derived TiO2 thin films

Sol-gel TiO₂ films were deposited from various sols and heat-treated at different temperatures. Fourier transform infrared spectroscopy, ellipsometry, X-ray diffraction, and scanning electron microscopy methods have been used to study physico-structural properties of the films. These properties are discussed with respect to the experimental parameters. It is shown that, depending on sol formulations and annealing temperatures, a large range of crystallite size, crystallization degree, film porosity, and surface morphology can be covered. The photocatalytic properties of the films have been studied in relation to their physico-structural properties through the photodecomposition of malic acid. This study shows that the photocatalytic activity undergoes a complex dependence on the physico-structural properties.     

Preparation and photocatalytic activity of N-doped TiO2 nanotube array films

The N-doped TiO₂ nanotube array films were fabricated directly by one-step electrochemical anodic oxidation of Ti foils in an HF electrolyte containing ammonium and nitrate ions. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDX), and ultraviolet–visible (UV–vis) absorption spectroscopy, respectively. The photocatalytic activities were evaluated by the degradation of methyl orange (MO) under visible light irradiation. The results showed that N dopant was successfully introduced into the TiO₂ nanotube array films. The N-doped TiO₂ nanotube array films showed a red shift and an enhancement of the absorption in the visible light region compared to the undoped sample. The photocatalytic activities of the N-doped TiO₂ samples were much higher than those of the undoped sample. A maximum enhancement of photocatalytic activity was achieved for the N-doped TiO₂ sample prepared in 0.07 M HF electrolyte containing 1.0 M NH₄NO₃, and 81% of MO was degraded in 150 min under visible light irradiation.     

Visible-light absorption and photocatalytic activity of Cr-doped TiO2 nanocrystal films

Chromium doped titanium dioxide (TiO₂) nanocrystal films with various doping concentration have been successfully prepared by a sol–gel dip-coating process. These films have been characterized by XRD, XPS, AFM, and UV–vis absorption spectroscopy. It is found that Cr doping can effectively reduce the transition temperature of anatase to rutile phase as well as the grain size. The absorption edges of TiO₂ thin films shift towards longer wavelengths (i.e. red shifted) from 375 nm to about 800 nm with increasing Cr concentration, which greatly enhances TiO₂ nano-materials on the absorption of solar spectrum. The appearance of UV–vis absorption features in the visible region can be ascribed to the newly formed energy levels such as Cr 2p level and oxygen vacancy state between the valence and the conduction bands in the TiO₂ band structure. The enhancement of the photocatalytic properties is observed for Cr-doped TiO₂ thin film.     

Photoactive TiO2/CuxO composite films for photocatalytic degradation of methylene blue pollutant molecules

Applying photocatalysts for utilizing solar energy is attractive because of its clean and limitless characteristics, but they have giant obstacles such as wide bandgaps, photocorrosion, and rapid charge recombinations to overcome for applications. In this study, the TiO₂/Cu_xO composite films are investigated as photoactive materials for the photodegradation ofmethylene blue (MB) pollutant molecules under standard sun light illumination. The TiO₂ layer is firstly fabricated on the FTO substrate by a doctor blade method, and then the second copper component is introduced by a spin-coating. Then, the composite films are thermally sintered to form cuprous and cupric oxides. This additional copper oxide phases plays a crucial role in achieving high photodegradation performance of MB under light irradiation. The best MB photodegradability from the TiO₂/Cu_xO composite films was achieved with the 3.6 wt% Cu_xO content case, and it is probably due to the effective charge separations with reduced recombinations in the copper oxide phases by the Z-scheme band arrangements between Cu₂O and CuO components. The composite films were characterized with scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV–visible spectroscopy for the film surface and cross-sectional morphology, crystalline structure, atomic binding energy, and light absorbance, respectively.     

Effects of mineral tourmaline particles on the photocatalytic activity of TiO2 thin films

Titania composite thin films (T/TiO2) containing tourmaline particles were prepared by a sol-gel method, using alkoxide solutions as precursor. The tourmaline particles and thin films were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and so on. The effects of tourmaline on the photocatalytic activity of TiO2 were measured with methyl orange as an objective photodegradation substance. The results showed that the photocatalytic degradation of methyl orange conformed to the first-order kinetic equation and the composite thin films had better photocatalytic activity due to the cooperation of polarity and the far infrared emission of tourmaline. The T/TiO2 thin films including 0.5 wt% tourmaline exhibited better photocatalytic activity when heat-treated at 250 degrees C for 3 h, than pure TiO2 thin films under the ultraviolet irradiation.     

Influence of gamma-irradiation on the photocatalytic activity of Degussa P25 TiO2

The purpose of this article is to study the influence of gamma irradiation on the sorption capacity and photocatalytic activity of commercially available TiO₂ Degussa P25. The photocatalyst was gamma-irradiated at ambient temperature with doses 8–60 kGy (¹³⁷Cs, dose rate 2 kGy/24 h) and then stored until analysis/tests in liquid N₂. X-ray diffraction, SEM, TEM, EPR, and UV–VIS reflectance spectrometry were applied to explore phase composition, crystal cell parameters, crystallite size, textural properties (grain size, and specific surface area), the presence of paramagnetic centers, and UV/VIS absorption of the initial and irradiated samples. The sorption capacity and photocatalytic activity of the products under UVA (17 W, λ _max = 365 nm) and sunlight irradiation were studied against Malachite Green 10⁻⁵ M aqueous solution, applied as a model pollutant. The sorption capacity varied non-monotonically with the irradiation dose, with clearly expressed maximum and minimum seen at irradiation with doses of 28 and 60 kGy, respectively. The maximum in the photocatalytic activity, both at UV and sunlight illumination, is observed after the dose of 28 kGy is applied; at these conditions, the pollutant degradation rate constant is 1.7/2.7-times higher than the value for the non-irradiated product. The explanation of the obtained results is related mainly to the type and concentration of gamma-generated defects in catalysts, and especially the effect of Ti³⁺ is discussed. Some of the considered factors may act in opposite directions, causing an extreme point in the relation between the photocatalytic activity and the gamma radiation dose.     

Facile synthesis of defected TiO2-x (B) nanosheet/graphene oxide hybrids with high photocatalytic activity

TiO2 (B) nanosheets/GO (graphene oxide) hybrids are considered to be outstanding performance pho-tocatalysts for high efficiency of H2 evolution.However,they still suffer severe challenges during the synthetic processes,such as a large amount of the capping agents adhering on the surface and easy occurrence of aggregation.To figure out these obstacles,Ar plasma treatment as a modified method in this study not only enable the TiO2 (B) nanosheets distributed uniformly on the GO sheets but also engi-neer defects within TiO2 (B) nanosheetsto significantly improve the photocatalytic activity for the water splitting.The hydrogen evolution rate of the TiO2-x (B)/GO sheets is 1.4 times higher compared with that of original TiO2 (B)/GO sheets without Ar plasma treatment.The improved photocatalytic proper-ties were owing to the synergetic effects of oxygen vacancies and the heterojunction between GO and TiO2 (B),which can promote the visible light utilization and accelerate separation and transportation of photogenerated electron-holes.This study can provide a facile pathway to prepare the two-dimensional hybrid photocatalysts with high photocatalytic H2 activity.     

TiO2功能薄膜的制备及影响其光催化活性的因素

近些年来，TiO2功能薄膜以其卓越的性能，尤其是优异的光催化性能引起研究人员的广泛关注，本文根据国内外近期TiO2功能薄膜的研究现状，对化学气相沉积法，水解一沉淀法，液相沉积法，溶胶－凝胶法，原子层沉积法，溅射法，激光辅助分子束沉积法等化学和物理制备方法进行评述，并比较详细地探讨了表面羟基含量，膜的厚度和孔径，结晶形态，基片种类，掺杂和光强度等因素对TiO2薄膜光催化性能的影响。     

玻璃固载TiO2/纳米纤维素复合薄膜的制备及其光催化性能

将微晶纤维素溶解于NaOH-尿素的低温溶液中形成纤维素溶液,在水浴中再生形成纳米纤维素溶液.然后将纳米纤维素溶液与TiO2(P25)混合,并添加少量的钛酸正丁酯作为交联剂形成复合溶液.将制备得到的复合溶液通过流延法固载到玻璃片表面形成玻璃固载的TiO2/纳米纤维素复合膜.通过SEM、XRD表征了复合膜的形貌与结构.将玻璃固载的TiO2/纳米纤维素复合膜在紫外光下进行光催化降解甲基橙(MO)以评估复合膜的光催化性能,研究了纳米TiO2含量对复合膜光催化性能的影响,复合膜的重复使用性能以及光降解的动力学过程.结果表明:复合膜对MO的光催化降解能力可达90％以上,与纯TiO2粉末相当,并重复使用3次光催化性能基本保持不变.复合膜对甲基橙的降解动力学符合一级动力学特征.当纳米TiO2相对于纤维素的质量分数为33.3％时,光催化活性最高,动力学速率常数为0.035min-1.     

光催化TiO2薄膜的溅射沉积技术

采用直流反应溅射技术可以制备出具有光催化作用的TiO2薄膜.这种TiO2薄膜经紫外光辐照后,可以分解有机物以及降低水和TiO2薄膜表面之间的接触角.然而,普通的直流反应溅射在制备介质膜时,普遍都存在着工艺不稳定、沉积速率低的问题,所以它不适合于工业化生产.脉冲磁控溅射与直流磁控溅射相比,它在基体表面附近具有较高的等离子体密度以及带电粒子具有较高的能量,这对于TiO2在低温下结晶十分有利.此外,采用双极脉冲模式生长的TiO2薄膜,它的光催化特性要优于单极脉冲模式.这种双极脉冲溅射并结合等离子体发射监控(PEM),使得工艺稳定性得到了改善,沉积速率亦得到了提高.     

Enhanced photocatalytic activity of C-N-codoped TiO2 films prepared via an organic-free approach

An organic-free sol-gel method was developed to synthesize crack-free, high surface roughness and visible-light-active C-N-codoped TiO(2) films. These films were subsequently evaluated for its photodegradation efficient using stearic acid as the model pollutant compound. The current approach avoids the use of hazardous organic solvents and employs carbon black as the carbon source as well as a template to increase the surface roughness. The presence of carbon and nitrogen species in TiO(2) was studied and discussed. The concentrations of carbon and nitrogen dopants in the TiO(2) films were affected by calcination temperature and the concentration of carbon black. Optimal visible light photocatalytic activity was observed for C-N-codoped TiO(2) film at 10.0 wt.% C, which was more than double that of the N-doped TiO(2) film. The enhancement in visible light photocatalytic activities of the C-N-codoped TiO(2) films was attributed to the synergistic effects of carbon and nitrogen dopants, and high surface roughness of the prepared films.     

Influence of oxygen flow rate on photocatalytic TiO2 films deposited by rf magnetron sputtering

Titanium dioxide (TiO₂) thin films having anatase (1 0 1) crystal structure were prepared on non-alkali glass substrates by rf (13.56 MHz) magnetron sputtering using a TiO₂ ceramic target under various oxygen partial pressures. At a fixed substrate temperature of 400 °C and total gas pressure of 1 Pa after 3 h deposition. Effects of oxygen partial pressure on the structural, surface morphology, and photocatalytic activities of the TiO₂ thin films were investigated. We performed both photoinduced decomposition of methylene blue (MB) and photoinduced hydrophilicity under UV light illumination. The XRD patterns exhibited a broad-hump shape indicating the amorphous structure of TiO₂ thin films. The results showed that when the [O₂/(Ar + O₂)] flow rate increased to 50%, the photoinduced decomposition of MB and photoinduced hydrophilicity were enhanced. The water contact angle after 9 min UV illumination was approximately 4.5°, and the methylene blue (MB) solution decomposition from 12 down to 3.34 μ mol/L for 240 min UV irradiation.     

Influence of structure parameters and crystalline phase on the photocatalytic activity of TiO2 nanotube arrays

Titanium oxide nanotube arrays (TiO2-NTAs) with different diameters and lengths are prepared by anodization of titanium foils in a water/ethylene glycol solution (5:95 V/V) containing 0.3 wt% NH4F. The effects of the diameters, lengths and crystalline phases of the NTAs on the photocatalytic (PC) activity are systematically evaluated. Larger pore diameter results in higher PC activity. The PC activity increases initially and then decreases with lengths for TiO2-NTAs and the optimal length that yields the highest PC activity is observed to be 6.2 microm. The crystalline phase and corresponding PC activity depend on the calcination temperature and their relationship is also investigated. The amorphous-to-anatase and anatase-to-rutile phase transitions initially occur at 300 and 500 degrees C, respectively. The PC activity of TiO2-NTAs initially increases with calcination temperature from 250 to 500 degrees C and then decreases at higher calcination temperature. The enhanced PC activity observed from the samples annealed at 250-450 degrees C is attributed to the better anatase crystalline structure at higher calcination temperature. The highest PC activity with regard to photodecomposition of methyl orange is observed from TiO2-NTAs calcined at 500 degrees C, which coincides with the anatse-to-rutile phase transformation. The synergistic effect of the anatase TiO2-NTAs and rutile barrier layers facilitate interfacial electron transfer consequently enhancing the PC activity. Further elevation of the calcination temperatures to 550 and 600 degrees C exhibits diminished PC activity because the NTs become shorter due to conversion of the bottom of anatase NTs into rutile film.     

Atomic layer deposition of TiO2 thin films on glass fibers for enhanced photocatalytic activity

Photocatalytic wastewater treatment is expected to become a sustainable way of eliminating toxic chemicals. Due to the surface-driven mechanism of the photocatalysis, surface area of the catalyst material plays a crucial role in the efficiency of the process, which is usually achieved by nanoparticles. However, using powder materials introduces a new problem: removing the catalyst materials out of clean water. As an alternative, atomic layer deposition (ALD) can form conformal thin films on high surface area substrates providing an immobilization route with high photocatalytic activity. Textile materials are inexpensive and accessible therefore good candidates for the substrate materials. Here, we deposit thin films on TiO₂ on fiberglass fabrics and investigate the photocatalytic activity. Since the as-deposited ALD TiO₂ films are amorphous, they have very limited photocatalytic activity. Upon thermal treatment of the films after deposition, photocatalytic activity is achieved. After four hours of exposure to the solar simulator and UV lamp, TiO₂-coated fibers demonstrated much higher photocatalytic activity than films on planar substrates previously described in the literature. The photocatalytic activity and structure of the coated fibers were investigated using XRD, XPS, UV–Vis, and PL analyses.

     

Influence of calcination parameters on the TiO2 photocatalytic properties

Nanocrystalline titanium dioxide (TiO₂) powders with different crystal phase composition were obtained by controlled hydrolysis and post-thermal treatments. The physicochemical properties of the powders were investigated by XRD, TEM/EDS, N₂ physic adsorption and DRS. The results obtained show that the particle size and crystalline structure are parameters strongly dependent on the calcination conditions, mainly temperature and heating rate. The influence of the TiO₂ phase composition on its photocatalytic activity, concerning the methylene blue photodegradation was studied. It was found that higher TiO₂ photocatalytic activity is related with the co-existence of the three TiO₂ polymorphs: anatase, brookite and rutile.