Facile fabrication, characterization, and enhanced photoelectrocatalytic degradation performance of highly oriented TiO2 nanotube arrays

Highly ordered TiO₂ nanotube arrays were successfully fabricated using ethanol and water mixture electrolytes (40 vol% ethanol and 0.2 wt% hydrofluoric acid) by a facile electrochemical anodization method. The as-prepared nanotube arrays were grown perpendicular to the titanium substrate with about 90 nm in diameter, 20 nm in wall thickness, and around 500 nm in length. The formation mechanism of the samples is briefly discussed. A blue shift in the spectrum of UV–Vis absorption was observed with respect to a piece of the sol–gel derived TiO₂ film. Moreover, photocurrent response and photoelectrocatalytic degradation of methyl orange under ultraviolet light irradiation were adopted to evaluate the photoelectrocatalytic properties of the TiO₂ nanotube arrays. We demonstrate that the highly ordered TiO₂ nanotube arrays possess much better photoelectrocatalytic activity than the sol–gel derived TiO₂ film and good stability.     

Photocatalytic activity enhancement of Dy-doped TiO2 nanoparticles hybrid with TiO2 (B) nanobelts under UV and fluorescence irradiation

The main drawbacks of anatase titanium dioxide (TiO₂) nanoparticles for being used as a photocatalyst are due to the rapid charge recombination of the electron-hole pairs and the wide band gap energy, limiting its photocatalysis application. To enhance photocatalytic activity, structure modification was performed here. Heterogeneous nanostructure of Dy-doped TiO₂ nanoparticles hybrid with Monoclinic TiO₂ nanobelts (Dy/TNBs) was fabricated via hydrothermal method. Annealing temperature was varied to investigate its effect on phase composition and morphology of the as-prepared TiO₂ catalyst. Phase composition and morphology were studied by XRD and SEM, respectively. The effect of amount of catalyst loaded on the degradation efficiency of methylene blue (MB) dye in aqueous solution under UV and fluorescence illumination was investigated. The results showed that pure monoclinic TiO₂ nanobelts (TNBs) was achieved at 450 °C. Enhanced photocatalytic activity under both UV and fluorescence irradiation was found on Dy/TNB samples. The optimum Dy dosage providing the highest MB degradation rates under both irradiation sources was 0.1 mol%.     

Preparation and characterization of Cobalt Sulfophthalocyanine/TiO2/fly-ash cenospheres photocatalyst and study on degradation activity under visible light

Cobalt Sulfophthalocyanine (CoSPc) sensitized TiO₂ sol samples were prepared through a Sol-Gel method using Cobalt Sulfophthalocyanine as a sensitizer. Loading and modified floating photocatalyst was prepared by hydrothermal method using fly-ash cenospheres as a carrier. The properties of the samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and UV-vis diffuse reflectance spectrum (DRS). Photocatalytic activity was studied by degrading wastewater of methylene blue under visible light. The results indicate that the fly-ash cenospheres are covered by modified TiO₂ film which composed of the anatase, brookite and rutile misch crystal phase. CoSPc/TiO₂/fly-ash cenospheres samples have good catalytic activity under visible light, and have strong absorbency during 600-700 nm. The sensitization of CoSPc can enhance visible light catalytic activity of TiO₂/fly-ash cenospheres. The degradation rate of methylene blue reaches 73.36% in 180 min under the visible light illumination. But too much CoSPc can decrease its catalytic activity.     

Effect of N2 ion flux on the photocatalysis of nitrogen-doped titanium oxide films by electron-beam evaporation

Nitrogen-doped titanium oxide (TiO_xN_y) films were prepared with ion-assisted electron-beam evaporation. The nitrogen (N) incorporated in the film is influenced by the N₂ flux modulated by the N₂ flow rate through an ion gun. The TiO_xN_y films have the absorption edge of TiO₂ red-shifted to 500 nm and exhibit visible light-induced photocatalytic properties in the surface hydrophilicity and the degradation of methylene blue. The structures and states of nitrogen in the films are investigated by X-ray diffraction patterns (XRD), and X-ray photoelectron spectroscopy (XPS) and related to their visible light-induced photocatalytic properties. The results indicate that the substitutional N in anatase TiO₂ can induce visible light photocatalysis. The substitutional N is readily doped by the energetic nitrogen ions from the ion gun. The best photocatalytic activity is obtained at the largest N loading about 5.6 at.%, corresponding to the most substitutional N in anatase TiO₂. The film exhibits the degradation of methylene blue with a rate-constant (k) about 0.065 h⁻¹ and retaining 7° water contact angle on the surface under visible light illumination.     

Highly ordered anodic TiO2 nanotube arrays and their stabilities as photo(electro)catalysts

Highly ordered TiO₂ nanotube arrays with an average diameter of 230 nm, a wall thickness of 30 nm and a length of 1.8 μm were fabricated within a large domain by electrochemically anodizing of a titanium foil in a mixed solution of glycerol and NH₄F aqueous electrolyte. The TiO₂ nanotubes exhibit an anatase structure after annealing at 450 °C in air for 3 h. The direct photolysis (DP), photocatalytic (PC), electrocatalytic (EC) and photoelectrocatalytic (PEC) activities of the TiO₂ nanotube arrays were investigated using methyl orange (MO) as the model pollutant. The degradation of MO in PC process is faster than that in DP process, which confirms the photocatalysis of TiO₂ nanotube arrays. The degradation rate in PEC process is much higher than those in EC and PC processes, which demonstrates the synergetic effect between PC and EC processes. The synergetic factor is 4.1, which suggests that the synergetic effect is strong. Moreover, the stabilities of morphology, structure and photo(electro)catalytic degradation performance of the TiO₂ nanotube arrays were studied in order to evaluate their applicability as photo(electro)catalysts. The photo(electro)catalytic experiments bring neither morphological nor structural modifications to the nanotube arrays. The photo(electro)catalytic degradation rates of the TiO₂ nanotube arrays maintain stable in 10 cycles, which indicates that the TiO₂ nanotube arrays are appropriate to be applied as photo(electro)catalysts.     

Photocatalytic degradation of methylene blue in water solution by multilayer TiO2 coating on HDPE

A multilayer photocatalytic TiO₂ coating on a high-density polyethylene (HDPE) disk was found to degrade aqueous methylene blue in a batch reactor study. The TiO₂ coating was fabricated by a low-temperature method using polyurethane resin (PU) as a barrier layer for HDPE and as a binding agent for two TiO₂ layers. Adequate adhesion between the HDPE substrate and PU barrier in aqueous environment was ensured with an oxygen plasma treatment.The photocatalytic effect of immersed TiO₂ coating on the degradation of methylene blue in aqueous solution was monitored by UV–vis spectrometry as a function of UV-illumination time. Samples were allowed to adsorb methylene blue in the dark for 1 h before the UV-degradation experiments were started. The percentages of methylene blue degraded during 6 h UV illumination (λ = 365 nm) varied from 80% to 92%. The degradation followed pseudo-first order reaction kinetics, and the observed rate constants (k_obs) were between 0.27 and 0.43 h⁻¹.     

Effect of Particle Size and Phase Composition of Titanium Dioxide Nanoparticles on the Photocatalytic Properties

Titanium dioxide (TiO₂) nanoparticles were prepared by the oxidation of titanium tetrachloride (TiCl₄) in a diffusion flame reactor. The average diameter of particles was 15–30 nm and mass fraction of anatase ranged from 40% to 80%. Effects of particle size and phase composition of those TiO₂ nanoparticles on photocatalytic properties such as decomposition of methylene blue, bacteria and ammonia gas were investigated. The degree of decomposition of methylene blue by the TiO₂ nanoparticles under the illumination of the black light was directly proportional to the anatase mass fraction, but inversely to the particle size. The decomposition of bacteria and ammonia gas by the TiO₂ nanoparticles under the illumination of the fluorescent light showed the same trend as in the case of the methylene blue.     

Preparation and photocatalytic property of CeO2 lamellar

A novel room temperature solid-state chemical synthesis was introduced to successfully fabricate CeO₂ samples, coupled by a polyethylene glycol 400 (PEG 400)/cetyl trimethylammonium bromide (CTAB)/sodium dodecyl sulfate (SDS). The as-prepared products were characterized by XRD, TEM, SEM, BET and UV. A study of photocatalytic degradation of the methylene blue MB under UV illumination has been carried out. It is indicated that the samples exhibit excellent photocatalytic activity. Besides, the samples assisted with surfactants possess higher photocatalytic activity than the sample without any surfactants, wherein the sample with SDS as an additive shows the highest photocatalytic activity, which is able to reach 89.6% MB degradation ratio within 60 min illumination. Moreover, the effects of important operational parameters such as initial MB concentration, catalyst loading and pH were also investigated. The above sample under the optimum conditions obtained the maximum MB degradation ratio up to 96.5%, which is higher than that of the commercial TiO₂ P25 under the same conditions. It can be concluded that CeO₂ will be a potential photocatalyst in the application of organic pollutant.     

Remarkably enhanced photocatalytic activity by sulfur-doped titanium dioxide in nanohybrids with carbon nanotubes

TiO₂ doped S nanohybrids with carbon nanotubes (CNTs) were synthesized with CNTs, thiourea and TiO₂ nanoparticles. The result indicated that the TiO₂ nanoparticles with about 8 nm in size are attached on the sidewall of CNTs. The nanohybrids material can absorb at longer wavelength and the absorption even covers the whole range of visible region than that only TiO₂ nanoparticles. Application of the catalysts to photocatalytic degradation of methylene blue (MB) was tested under visible light irradiation. The result suggests that a high MB degradation activity of S-TiO₂/CNTs due to a reduce band gap of TiO₂ when S is doped, and the decrease in the possibility of electron–hole recombination by CNTs. In addition, the density functional-theory (DFT) calculations of the electronic band structures and density of states (DOS) to understand the bonding states between TiO₂ and CNTs, proved that the TiO₂/CNTs system is stable.     

Fabrication of Ag/TiO2 nanotube array with enhanced photo-catalytic degradation of aqueous organic pollutant

In this paper, the fabrication of Ag/TiO₂ nanotube arrays and their photo-catalytic activity have been studied. The SEM, TEM and XRD were performed to characterize the morphology and crystalline phase of the TiO₂ nanotube array and Ag/TiO₂ nanotube array. Ag nanoparticles with different loadings, which are aimed to suppress the electron–hole recombination so as to enhance the photo-catalytic oxidation efficiency, were systematically coated onto TiO₂ nanotubes. The photo-catalytic activity of these nano-materials was evaluated by the degradation of two different pollutants: methyl orange and glyphosate. The effects of various parameters, such as the amount of the photo-catalyst, the illumination time, and pH value on the photo-catalytic oxidation activity, were studied.     

Photocurrent enhancement of heat treated CdSe-sensitized titania nanotube photoelectrode

The self-organized titania nanotube arrays (NTAs) fabricated by anodisation has gained enormous interest due to its high spatial orientation, excellent charge transfer structure, and large internal surface area; all are crucial properties influencing the absorption and propagation of light. In this study, a composite material, CdSe nanoparticle/TiO₂ nanotube arrays (CdSe/TiO₂ NTAs) were assembled through the insertion of CdSe nanoparticles onto the anodized TiO₂ nanotube arrays via electrochemical deposition. The annealing temperature of CdSe/TiO₂ NTAs was varied from 200 to 350 °C and was found to play an important role in controlling the formation of CdSe nanoparticles on TiO₂ NTAs. Characterizations of the films were performed by using field emission scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, high resolution transmission electron microscopes, X-ray diffractometry and UV–visible diffuse reflectance spectroscopy. The transient photocurrent was examined in a three-electrode system under halogen illumination by using the prepared film as the photoanode. It was found that the CdSe nanoparticles were susceptible to spread through electrochemical deposition and formed on the nanotubes by annealing in nitrogen atmosphere. The increment in annealing temperature has resulted in greater amount of CdSe loaded onto TiO₂ nanotube arrays. Therefore, a suitable annealing temperature can enhance the particle interaction, leading to considerable improvement in PEC performance. The sensitized CdSe/TiO₂ NTAs annealed at 250 °C displayed 84 folds improvement in photoconversion efficiency than that of bare TiO₂ NTAs counterparts.     

Efficient visible light-induced photoelectrocatalytic degradation of rhodamine B by polyaniline-sensitized TiO<Subscript>2</Subscript> nanotube arrays

Self-organized anodic TiO₂ nanotube arrays were sensitized with polyaniline by a simple electrodeposite method. The morphological and structural properties studied by scanning electron microscopy and fourier transform infrared spectroscopy reveal the successful deposition of polyaniline on the nanotube arrays. The polyaniline-sensitized TiO₂ nanotube arrays exhibit a distinguishable red shift on the absorption spectrum. Electrochemical impedance investigation attested to a significant improvement of the interfacial electron-transfer kinetics for promoted electron–hole effective separation. The as-prepared samples showed a high efficiency for the photoelectrocatalytic degradation of rhodamine B under visible-light irradiation (λ > 400 nm). The enhanced photoelectrocatalytic activity could be attributed to the extended absorption in the visible-light region by the polyaniline and the effective separation of photogenerated carriers driven by the photoinduced potential difference generated at the polyaniline/TiO₂ nanotube arrays interface.     

Photocatalytic Activities of Boron Doped Titanium Dioxide Nanoparticles and its Composite with Polyaniline

Abstract

Titanium dioxide (TiO₂) was doped with a nonmetalic element, boron (B), and the boron doped TiO₂ (B-TiO₂) was combined with polyaniline (Pani) through an in-situ polymerization technique. The photocatalytic activity of the prepared samples was monitored by the degradation of methylene blue under UV light irradiation. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to reveal the effect of boron doping on the crystalline and chemical structure of the photocatalyst, respectively. The morphological and elemental compositional characteristics of the samples were evaluated using field emission scaning electron microscopy (FE-SEM) and energy dispersive x-ray analysis. The optical band gap energy of the prepared samples was obtained by UV-Visible (UV-Vis) spectroscopy. B-TiO₂ exhibited enhanced photocatalytic performance compared to the undoped photocatalyst. Furthermore, compared with TiO₂ and B-TiO₂, Pani/B-TiO₂ displayed superior photocatalytic activity. The composite achieved almost 26% methylene blue degradation within 150?minutes. Although the boron doping enhanced the crystallinity of TiO₂ slightly, it did not affect the morphology. FTIR confirmed the presence of tri-coordinated interstitial boron in the Ti–O–B bonds. The UV-Vis spectra displayed a red shift with the incorporation of the boron atoms. The incorporation of the boron atoms in the TiO₂ crystal structure are suggested to promote the separation of the photoinduced electron-hole pairs, a possible reason for the enhanced photocatalytic activity. B-TiO₂ and its composite with polyaniline could be considered as a promising photocatalyst to remove organic dyes from the wastewater.     

A study on photo-generated charges property in highly ordered TiO2 nanotube arrays

In this study TiO₂ nanotube arrays were fabricated by potentiostatic anodization of titanium sheet. The X-ray diffraction (XRD) pattern and field emission scanning electron microscopy (FE-SEM) image indicated the TiO₂ nanotube arrays were of pure anatase form and highly ordered. The properties of the photo-generated charges in the nanotube arrays were investigated by transient photovoltage (TPV) technique and surface photovoltage (SPV) technique based on lock-in amplifier with dc bias, in comparison with the commercial powder derived film. The separation processes of the photo-induced charges in the system of TiO₂ nanotubes on Ti have been demonstrated to be correlated with the incident light intensity, surface trapping states, and the interfacial electric field between Ti and TiO₂. The results also show that the highly ordered nanotube film could generate much stronger SPV responses under external electric field than the commercial powder derived film.     

Enhanced photocatalytic activity and stability of nano-scaled TiO2 co-doped with N and Fe

Titanium dioxide (TiO₂) nanoparticles co-doped with N and Fe were prepared via modified sol-gel process. The products were characterized by transmission electron microscopy (TEM), N₂ adsorption, X-ray diffraction (XRD), Raman spectroscopy, UV-vis spectroscopy, photoluminescence (PL), and X-ray photoelectron spectroscopy (XPS). It is shown that the prepared TiO₂ particles were less than 10 nm with narrow particle size distribution. The addition of MCM-41 caused the formation of Ti-O-Si bond which fixed the TiO₂ on MCM-41 surface, thus restricted the agglomeration and growth of TiO₂ particles. The photocatalytic performance in the degradation of methylene blue showed that N, Fe co-doped TiO₂ exhibited much higher photocatalytic activity than doped sample with nitrogen or Fe³⁺ alone under both UV and visible light. N, Fe co-doping decreased the loss of doping N during the degradation reaction, thus increased the photocatalytic stability. It was also found that the nitridation time had significant influence on the photocatalytic activity of prepared TiO₂ catalysts.     

Ni-doped TiO2 nanotube arrays on shape memory alloy

Self-organized Ni-Ti-O nanotube arrays were fabricated through a direct anodization of NiTi shape memory alloy in glycerol-based electrolyte. The growth of Ni-doped TiO₂ nanotube arrays was mainly affected by anodization voltage and temperature. Higher anodization voltage facilitated the growth of uniform nanotube arrays. Large-area open-ended Ni-Ti-O nanotube arrays could form on the surface of the shape memory alloy under a higher anodization temperature. The oxide nanotubes had a gradually changed composition along the growth direction of the nanotube and presented a thermal stability up to 400 °C. The nanotubular oxide demonstrated a much better hydrophilic behavior than that of the traditional oxide layer grown on NiTi substrate through air oxidization. The successful fabrication of Ni-doped TiO₂ nanotube arrays here makes it feasible to further explore excellent physical and chemical as well as biomedical properties of the nanotube-modified surfaces of the NiTi shape memory alloy.     

Photocatalytic properties of porous C-doped TiO2 and Ag/C-doped TiO2 nanomaterials by eggshell membrane templating

Porous organic carbon-doped titania (C-TiO₂) nanomaterials and their composites with Ag nanoparticles (Ag/C-TiO₂) were synthesized by an eggshell membrane templating method, and their structural and photocatalytic properties were systematically characterized. These nanomaterials, exhibiting a macroscopic morphology of a thin film, are composed of interwoven tubes, and the tube wall consists of nanocrystals. The doped organic carbon was composed of the active carbon and carbonate species, which could form a layer around the surface of TiO₂ nanoparticles, while the silver was incorporated into Ag/C-TiO₂ composites as separated Ag nanoparticles. The degradation of methylene blue under visible light irradiation was employed to evaluate the photocatalytic activity of these as-prepared TiO₂-based materials. Both C-TiO₂ and Ag/C-TiO₂ nanomaterials showed higher photocatalytic activity than pure TiO₂ material–commercial Degussa P25. These results can be accounted for the coupling effect of the incorporation of carbon species and Ag nanoparticles.     

Photocatalytic decomposition of methylene blue and 4-chlorophenol on nanocrystalline TiO2 films under UV illumination: A ToF-SIMS study

The photocatalytic degradation of methylene blue and 4-chlorophenol on nanocrystalline TiO₂ (nc-TiO₂) under UV irradiation was investigated by time-of-flight secondary ion mass spectrometry (ToF-SIMS). Nanocrystalline TiO₂ films were prepared from suspensions containing TiO₂-crystallites of different average sizes, the smallest one being 12 nm. The organic substances (either methylene blue or 4-chlorophenol) were applied to these films. The specimens were studied in the pristine state and upon UV exposure. The UV illuminations were carried out both under atmospheric conditions and in situ under ultrahigh vacuum in the ToF-SIMS instrument. Distinct mass signals from the parent molecules and from fragment ions are observed for the as-prepared samples. Upon irradiation with UV light under atmospheric conditions, the surface composition is significantly changed, an observation ascribed to photocatalytic reactions induced by UV photons: the parent molecule signals are strongly diminished whereas fragmentation products are identified to be present at the TiO₂ surfaces. UV irradiations carried out under different vacuum conditions in the ToF instrument (ultrahigh vacuum, air or oxygen adsorption) indicate that varying ambient conditions may influence the photocatalytic reaction on the nanocrystalline TiO₂ films.     

Optical and structural properties of TiO<Subscript>2</Subscript> nanopowders with Ce/Sn doping at various calcination temperature and time

In this paper, the influence of calcination temperature and time has been investigated on the structural, morphological, optical, and photo-catalytic properties of Sn/Ce co-doped TiO₂ nano-powders prepared via sol–gel process. They were calcined at the temperatures in the range of 475–975 °C for 1 and 2 h. The photocatalytic ability of TiO₂ powders was evaluated by means of methylene blue degradation experiments conducted under the irradiation of simulated solar light. The X-ray diffraction results showed that the tensile strain in the host lattice was present. The comparison with undoped and Sn or Ce-doped TiO₂, co-doped TiO₂ shows an obviously higher catalytic activity under visible light irradiation. The absorbance spectrum of Ce and Sn co-doped TiO₂ exhibited significant red-shift to visible region. The red-shift is caused by the appearance of a new electronic state in the middle of the TiO₂ band-gap. FESEM images show the formation of doped TiO₂ nanoparticles with small size in structure and spherical in shape. The FTIR spectra exhibited peaks corresponding to the anatase and rutile structure phases of TiO₂.     

CuAPTPP-TDI-TiO2光催化微球的合成及其光催化性能 (cited: 1)

采用Adler法合成了5-(4-氨基苯基)-10,15,20-三苯基卟啉铜配合物(CuAPTPP),通过甲苯二异氰酸酯(TDI)的桥联作用对TiO₂微球进行表面修饰,使TDI分子中的两个活性TDI基团分别与TiO₂表面的羟基和CuAPTPP的氨基反应,将CuAPTPP敏化剂分子以化学键合的方式固定在TiO₂表面,形成光催化微球CuAPTPP-TDI-TiO₂．通过FT-IR、XRD、SEM、EA、UV-Vis和DRS等测试手段对CuAPTPP-TDI-TiO₂进行结构表征．讨论了桥联分子TDI修饰量对光催化微球性能的影响,确定了TDI与TiO₂的最佳摩尔比．以亚甲基蓝(MB)为降解对象,考察了CuAPTPP-TDI-TiO₂微球的可见光催化性能．结果表明,桥联分子TDI在CuAPTPP与TiO₂微球表面形成了牢固的化学键,复合微球在150 W氙灯辐照下降解10 mg/LMB溶液,120 min降解率可达98.7%,其降解率过程服从一级动力学规律,测得降解速率常数为5.1×10^-2 min^-1,半衰期为11.3 min．催化微球在回收4次的条件下,对MB的降解率仍保持在90%以上．