The effects of growth conditions on the surface properties and photocatalytic activities of anatase TiO<Subscript>2</Subscript> films prepared via electrochemical anodizing and annealing methods

In the present work, nanostructured TiO₂ films were prepared by electrochemical anodization process of titanium in fluoride-containing electrolytes using an innovative approach. After anodization, the TiO₂ films were annealed at 480?°C for 2 h in air in order to acquire anatase phase transformation and increase its crystallinity. The effects of anodization voltage, electrolyte concentration and anodization time on the formation of TiO₂ films and the photocatalytic degradation of methylene blue (MB) were discussed in details. The phase structure and surface morphology of the samples characterized by means of X-ray diffraction and scanning electron microscope. The as-prepared nanostructured TiO₂ film anodized in 0.5% HF electrolyte at 15 V for 240 min showed excellent photocatalytic degradation of MB and is promising for environmental purification.     

Efficient photocatalytic removal of aqueous Cr(VI) by N-F-Al tri-doped TiO<Subscript>2</Subscript>

As chromium is a common heavy metal contaminant in water, we have prepared N-F-Al tri-doped TiO₂ catalyst for Cr(VI) removal under visible light. The sample was prepared via a sol-gel method and was characterized by XRD, BET, UV-vis DRS, XPS and SEM techniques. In the photocatalytic experiments, effects of Al/Ti ratio, F/Ti ratio, calcination temperature and different dopants were investigated. The optimum Al/Ti molar ratio, F/Ti ratio and calcination temperature proved to be 0.01, 0.1 and 500 °C, respectively, which is in accordance with the characterization analysis. Catalysts prepared under this condition showed a high photoactivity for Cr(VI) removal in water.     

Fabrication of high aspect ratio and open‐ended TiO2 nanotube photocatalytic arrays through electrochemical anodization

Well‐aligned, high aspect‐ratio and open‐ended TiO₂ nanotube arrays secured within a Ti foil (TiO₂ nanotubes cartridge) were successfully prepared through the double‐sided anodization method. With ～210 µm of nanotube length, the anodic growth of TiO₂ was accelerated and stabilized by the lactic acid‐containing ethylene glycol electrolyte. In the absence of lactic acid, the anodization led to detachment of nanotubes from the Ti foil after 5–6 h of high voltage (80 V) anodization. Transmission electron microscope image and Raman spectrum revealed that the as‐anodized TiO₂ nanotube arrays without annealing treatment were partially crystalline anatase and demonstrated photocatalytic activity in the mineralization of formic acid. © 2015 American Institute of Chemical Engineers AIChE J, 62: 415–420, 2016     

Photo‐reduction and adsorption in aqueous Cr(VI) solution by titanium dioxide,carbon nanotubes and their composite

BACKGROUND: This study compared the removal of aqueous Cr(VI) by multi‐walled carbon nanotubes (CNTs) modified by sulfuric acid, titanium dioxide (TiO₂) and composite of CNTs and TiO₂. RESULTS: More than 360 h contact time was needed to completely adsorb 3 mg L^?1 of Cr(VI) by CNTs, indicating that the rate of adsorption by CNTs alone was slow. The reaction time approaching equilibrium depended on the Cr(VI) concentration. XPS analysis of CNTs after adsorbing Cr(VI) showed that the Cr(VI) on the surface of CNTs was partially reduced to Cr(III). A 3 mg L^?1 solution of Cr(VI) was fully photocatalyzed by commercial TiO₂ (Degussa P25) in less than 0.5 h under UV irradiation. Unlike P25, reduction by another commercial TiO₂ (Hombikat UV100) took 4 h and more than 2 h were necessary for reduction by the composite. Thus the efficiency of Cr(VI) photo‐reduction by the composite was lower than by TiO₂, but higher than that by CNTs. XPS analysis of TiO₂ and composite showed the existence of both Cr(VI) and Cr(III) on their surfaces. CONCLUSION: In contrast to TiO₂, the reduction rate of aqueous Cr(VI) using CNTs as adsorbent was slow. P25 had a markedly higher photocatalytic efficiency than the composite or UV100 alone. Using P25 to reduce aqueous Cr(VI) has a higher potential for practical application. The diameters of TiO₂ and CNTs and the ratio of TiO₂/CNTs are key problems in the preparation of TiO₂/CNTs composite. Copyright © 2011 Society of Chemical Industry     

Photo-electrochemical behavior at different wavelengths of electrochemically obtained TiO<Subscript>2</Subscript> nanotubes

The results of an experimental study on the photo electrochemical behavior of nanotubular TiO₂ structures are presented in this work. TiO₂ samples were prepared by electrochemical anodization of Ti foils and submitted to thermal annealing. The influence of the current transient during the anodization, and of the annealing temperature on the photochemical response of the samples at different wavelengths was studied. Different behavior of the samples was observed, which may be attributed to the distributions of defects and to their different sensitivity to the temperature. The analysis of the performance of the samples in absence or in the presence of glycerol, used as hole scavenger, provided more information on the photo-catalytic properties of these structures.     

Effect of microstructural evolution on wettability and tribological behavior of TiO2 nanotubular arrays coated on Ti–6Al–4V

Self-organized TiO₂ nanotubular arrays were fabricated by electrochemical anodization of Ti–6Al–4V plates in an NH₄F/H₃PO₄ electrolyte. The effect of microstructural evolutions on the wettability and tribological behavior of the TiO₂ nanotubes was investigated. Based on the XRD profiles of the fabricated material, the characteristic TiO₂ peaks were not recognized after anodization; however, highly crystalline TiO₂ (anatase and rutile) was formed due to crystallization during annealing at 500 °C for 1.5 h. The nanotube arrays were converted entirely to rutile at 700 °C. From a microstructure point of view, a highly ordered nanotube structure was achieved when the specimen was annealed at 500 °C, with a length of 0.72 μm and a pore diameter of 72 nm. Further increasing the annealing temperature to 700 °C resulted in the complete collapse of the tubular structure. The results indicate that the improved wettability of the anodized specimens was due to the combination of the effects of both the surface oxide layer and the increased surface roughness achieved after anodization. Moreover, the wear resistance and wettability of the sample annealed 500 °C were improved due to the high hardness (435 HV) and low coefficient of friction (0.133–168) of the highly crystalline structure of the TiO₂ nanotubes.     

A cylindrical core-shell-like TiO<Subscript>2</Subscript> nanotube array anode for flexible fiber-type dye-sensitized solar cells

A versatile anodization method was reported to anodize Ti wires into cylindrical core-shell-like and thermally crystallized TiO₂ nanotube (TNT) arrays that can be directly used as the photoanodes for semi- and all-solid fiber-type dye-sensitized solar cells (F-DSSC). Both F-DSSCs showed higher power conversion efficiencies than or competitive to those of previously reported counterparts fabricated by depositing TiO₂ particles onto flexible substrates. The substantial enhancement is presumably attributed to the reduction of grain boundaries and defects in the prepared TNT anodes, which may suppress the recombination of the generated electrons and holes, and accordingly lead to more efficient carrier-transfer channels.     

Effect of synthesis highly ordered TiO<Subscript>2</Subscript> nanotube arrays with enhanced photocatalytic properties by time,electrolytic voltage,heating temperature and Polyvinyl pyrrolidone

Highly ordered TiO₂ nanotube arrays were prepared by anodization method with doped Polyvinyl pyrrolidone (PVP) addition. The as-prepared samples were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD) and transmission electron microscopy. The results suggested that TiO₂ nanotubes arrays modified by 0.10 wt% PVP were better uniform and more highly ordered than that of pure TiO₂. The average inner diameter and the tube length of TiO₂ nanotubes were extended approximately 77 nm and 5.21 μm, respectively. Meanwhile, the optimum synthesis conditions (40 V, 4 h and 450 °C) were determined by SEM and XRD. In addition, the photocatalytic activity of the as-prepared samples was investigated for the degradation of RhB under UV-lamp irradiation. The results showed that almost 100 % of RhB was degradation within 80 min by the as-prepared nanotubes in the optimum synthesis conditions. It was indicated that the photocatalytic activity of the as-prepared nanotubes was improved greatly due to their well morphology, enhanced UV-light absorption property and electron transmission ability. In general, this study could provide a principle method to synthesize TiO₂ nanotube arrays with enhanced photocatalytic activity and improved microstructure by anodization process with PVP addition.     

Facile synthesis of robust free-standing TiO2 nanotubular membranes for biofiltration applications

Robust monodisperse nanoporous membranes have a wide range of biotechnological applications, but are often difficult or costly to fabricate. Here, a simple technique is reported to produce free-standing TiO₂ nanotubular membranes with through-hole morphology. It consists of a three-step anodization procedure carried out at room temperature on a Ti foil. The first anodization (1 h at 80 V) is used to pattern the surface of the metallic foil. Then, the second anodization (24 h at 80 V) produces the array of TiO₂ nanotubes that will constitute the final membrane. A higher voltage anodization (3–5 min at 180 V) is finally applied to detach the TiO₂ nanotubular layer from the underlying Ti foil. In order to completely remove the barrier layer that obstructs some pores of the membrane, the latter is etched 2 min in a buffered oxide etch solution. The overall process produces 60-μm-thick TiO₂ nanotubular membranes with tube openings of 110 nm on one side and 73 nm on the other side. The through-hole morphology of these membranes has been verified by performing diffusion experiments with glucose, insulin, and immunoglobulin G where in differences in diffusion rate are observed based on molecular weight. Such biocompatible TiO₂ nanotubular membranes, with controlled pore size and morphology, have broad biotechnological and biomedical applications.     

Two novel hierarchical homogeneous nanoarchitectures of TiO<Subscript>2</Subscript> nanorods branched and P25-coated TiO<Subscript>2</Subscript> nanotube arrays and their photocurrent performances

We report here for the first time the synthesis of two novel hierarchical homogeneous nanoarchitectures of TiO₂ nanorods branched TiO₂ nanotube arrays (BTs) and P25-coated TiO₂ nanotube arrays (PCTs) using two-step method including electrochemical anodization and hydrothermal modification process. Then the photocurrent densities versus applied potentials of BTs, PCTs, and pure TiO₂ nanotube arrays (TNTAs) were investigated as well. Interestingly, at -0.11 V and under the same illumination condition, the photocurrent densities of BTs and PCTs show more than 1.5 and 1 times higher than that of pure TNTAs, respectively, which can be mainly attributed to significant improvement of the light-absorbing and charge-harvesting efficiency resulting from both larger and rougher surface areas of BTs and PCTs. Furthermore, these dramatic improvements suggest that BTs and PCTs will achieve better photoelectric conversion efficiency and become the promising candidates for applications in DSSCs, sensors, and photocatalysis.     

Well-matched electrochemical performances of TiO<Subscript>2</Subscript> nanotubes based on Ti wires with strong adhesion to Ti substrate

Anodic TiO₂ nanotubes (ATNTs) fabricated by anodization of Ti foils have been investigated for many years due to unique structure and excellent electrochemical performance. However, nanotube arrays fabricated on Ti foils are prone to peeling, which is one of the critical defects for applications. To overcome this challenge, the nanotubes on Ti wires are fabricated for the first time, for which the cylinder shape can neutralize stress between ATNTs and Ti substrate. The influences of anodizing temperature and NH₄F concentration on morphology and electrochemical performances of ATNTs fabricated on Ti wires and Ti foils, are explored and compared in detail. There are many remarkable differences between anodization processes on Ti wires and Ti foils. The anodizing current density–time curves of ATNTs fabricated on Ti wires present a slow and stepwise decrease at the quasi-steady state and corresponding FESEM images show that ATNTs with numerous halfway-terminated nanotubes were growing in a radial direction on the circumference of Ti wires, much different from ATNTs fabricated on Ti foils. The electrochemistry behaviors (supercapacitor performance) of ATNTs fabricated on Ti wires and Ti foils were studied by cyclic voltammetry and galvanostatic charge–discharge tests. The results demonstrate that the nanotubes fabricated on Ti wires show stronger adhesion strength and stable performance, thus paving the way for the application of ATNTs.     

Boron doped titaniumdioxide nanotube arrays: production,characterization and photocatalytic properties

In numerous studies, regularly oriented anatase titanium dioxide nanotube arrays (TNTAs), obtained through electrochemical anodization, have been employed as catalyst surfaces for photocatalytical applications. However, in many practical applications the phocatalytical activities are restricted due to their wide band gaps. This work shows that photocatalytical activity of TNTAs can be improved by a novel approach which provides boron incorporation into TiO₂ structure during anodization process without any further treatment. Anodization was performed in an aqueous solution containing hydrofluoric acid, oxalic acid and sodium fluoroborate (NaBF₄) at room temperature on titanium (Gr2) substrates. The anodized samples were annealed at 480?°C for 2 h in air in order to obtain anatase transformation and intended crystalline structure. As-prepared B-doped TNT structure was characterized by field emission scanning electron microscope, energy dispersive X-ray spectroscopy, X-ray diffraction, atomic force microscopy and ultraviolet–visible light diffuse absorbance spectroscopy. The photocatalytic kinetics of B-doped TNTAs for the degradation of methylene blue (MB) under visible light irradiation were evaluated in details.     

Formation of Ti-Si composite oxide films on Mg-Al-Zn alloy by electrophoretic deposition and anodization

TiO₂ or SiO₂ nanoparticles dispersed in an acetone solvent containing iodine were deposited on Mg-Al-Zn alloy by electrophoretic deposition (EPD). Subsequently, the composite oxide films were formed on the substrate by anodization in KOH-Na₂SiO₃ aqueous solutions containing TiO₂ or SiO₂ nanoparticles. The films formed by EPD were improved binding with the substrate by anodization under high voltages with sparking, and then the anodic films consisted of Si-Mg or Ti-Si-Mg composite oxides. The film thicknesses of TiO₂ and SiO₂ on the alloy increased with anodization time. In polarization tests, the films anodized under high voltages with sparking in the alkaline solutions had high corrosion resistance. Thus, the composite oxide films formed in the present method were successful in providing corrosion resistance to Mg alloy.     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite oxide and its photocatalytic degradation of rhodamine B

The composite semiconductor photocatalyst TiO₂/SiO₂ was prepared by template-hydrothermal method using carbon spheres as the template. The structural and optical properties of TiO₂/SiO₂ were characterized by XRD, SEM, BET, UV–Vis DRS, TG-DTA, PL techniques. The formation of hydroxyl radical on the surface of TiO₂/SiO₂ was studied with terephthalic acid as the probe molecule, combined with fluorescence technique. The results showed that the specific surface area of TiO₂/SiO₂ composite was 327.9 m²/g, and the specific surface area of TiO₂/SiO₂ was larger than that of pure TiO₂. Photocatalytic degradation of rhodamine B showed that TiO₂/SiO₂ composite oxide under visible light illumination 40 min, the degradation rate was 98.6 % and the degradation rate of pure TiO₂ was only 11.9 %. The apparent first-order rate constant of TiO₂/SiO₂ was 33 times that of pure TiO₂ and more than 6 times that of P25 when the molar ratio of Ti to Si was 1:1 under visible light irradiation. Moreover, it’s also as much as 5 times that of pure TiO₂ and is more than 1 times that of P25 under UV light irradiation 25 min. Based on the experimental results, ^·O₂ ^? and h⁺ were suggested to be the major active species which was responsible for the degradation reaction. The increased photocatalytic activity of TiO₂/SiO₂ may be mainly attributed to effectively suppressing the recombination of hole/electron pairs. After the photocatalyst TiO₂/SiO₂ was reused 5 times, the degradation rate of rhodamine B could reach 89.2 % under visible light irradiation. Moreover, The composite semiconductor photocatalyst TiO₂/SiO₂ was selective towards the degradation of rhodamine B.     

Surface characterization and photocatalytic reactivity of innovative Ti/TiO2 and Ti/Pt−TiO2 mesh photoelectrodes

Novel Ti/TiO₂ and Ti/Pt–TiO₂ mesh photoelectrodes were produced by anodizing titanium mesh in H₂SO₄ solution. Their structural and surface morphology were examined by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The analytical results indicated that the crystal structure, morphology and pore size were affected significantly by the voltage and current density applied in anodization and the percentage platinum content. The results of XPS measurement showed that the binding energy of O 1s and Ti 2p increased slightly owing to platinum deposition (Pt⁰, Pt²⁺ and Pt⁴⁺) onto the TiO₂ surface. The photoelectrocatalytic (PEC) oxidation of methyl orange in aqueous solution using the Ti/TiO₂ and Ti/Pt–TiO₂ meshes was investigated. The experimental results demonstrated that Ti/TiO₂ mesh prepared at 160 V and 110 mA cm^–2 achieved the best PEC oxidation. The efficiency of PEC oxidation could be further enhanced by applying an electrical bias between the working electrode and counter electrode. An optimal electrical bias voltage was found to be 0.6 V, while an optimal platinum content was 3.37%.     

SnS2/TiO2 nanocomposites with enhanced visible light-driven photoreduction of aqueous Cr(VI)

SnS₂/TiO₂ nanocomposites have been synthesized via microwave assisted hydrothermal treatment of tetrabutyl titanate in the presence of SnS₂ nanoplates in the solvent of ethanol at 160 °C for 1 h. The physical and chemical properties of SnS₂/TiO₂ were studied by XRD, FESEM, EDS, TEM, XPS and UV–vis diffuse reflectance spectra (DRS). The photocatalytic activity of SnS₂/TiO₂ nanocomposites were evaluated by photoreduction of aqueous Cr(VI) under visible light (λ>420 nm) irradiation. The experimental results showed that the SnS₂/TiO₂ nanocomposites exhibited excellent reduction efficiency of Cr(VI) (~87%) than that of pure TiO₂ and SnS₂. The SnS₂/TiO₂ nanocomposites were expected to be a promising candidate as effective photocatalysts in the treatment of Cr(VI) wastewater.     

Alkali-free synthesis of a novel heterostructured CeO2-TiO2 nanocomposite with high performance to reduce Cr(VI) under visible light

In this study, a novel CeO₂-TiO₂ nanocomposite denoted as CeO₂-3TiO₂ was successfully synthesized via a facile one pot hydro-thermal method without alkali. It exhibits high photocatalytic reduction reactivity toward Cr(VI) under visible light. The photocatalytic reactivity of CeO₂-3TiO₂ is 18 times higher than that of pure CeO₂, 28 times higher than pure TiO₂, 15 times higher than the sample of simply mixed CeO₂ and TiO₂. The solution with Cr(VI) initial concentration of 2780 ppb can be fast photoreduced by CeO₂-3TiO₂ in 60 min under visible light to meet the criterion of U.S. Environmental protection Agency. Characterization results indicate CeO₂-3TiO₂ has the good crystal form of heterojunction structure, narrow pore size distribution, narrow energy gap and high photogenerated electron-hole separation efficiency. Based on the experimental results, a speculated photocatalytic mechanism was proposed.     

Effect of pre-nitridation treatment on the formation of anatase TiO2 films by anodization

High performance-anatase TiO₂ films were successfully formed on metallic titanium by anodization in an acidic electrolyte composed of H₂SO₄, H₃PO₄ and H₂O₂ subsequent to pre-nitridation treatment. The pre-nitridation treatment was carried out by pre-annealing metallic titanium under a nitrogen atmosphere of 0.1 MPa. The anodized films showed photocatalytic activity in photooxidization of the iodide anion into the tri-iodide anion. The nitridation treatment had a significant effect not only on the formation of anatase TiO₂ films but also on the photocatalytic activity of the anodized films.     

Removal characteristics of chromium by activated carbon/CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> magnetic composite and <Emphasis Type="Italic">Phoenix dactylifera</Emphasis> stone carbon

Activated carbon (AC) was synthesized from Phoenix dactylifera stones and then modified by CoFe₂O₄ magnetic nanocomposite for use as a Cr(VI) adsorbent. Both AC/CoFe₂O₄ composite and AC were fully characterized by FTIR, SEM, XRD, TEM, TGA, and VSM techniques. Based on the surface analyses, the addition of CoFe₂O₄ nanoparticles had a significant effect on the thermal stability and crystalline structure of AC. Factors affecting chromium removal efficiency like pH, dosage, contact time, temperature, and initial Cr(VI) concentration were investigated. The best pH was found 2 and 3 for Cr adsorption by AC and AC/CoFe₂O₄ composite, respectively. The presence of ion sulfate had a greater effect on the chromium sorption efficiency than nitrate and chlorine ions. The results illustrated that both adsorbents can be used up to seven times to adsorb chromium. The adsorption process was examined by three isothermal models, and Freundlich was chosen as the best one. The experimental data were well fitted by pseudo-second-order kinetic model. The half-life (t_1/2) of hexavalent chromium using AC and AC/CoFe₂O₄ magnetic composite was obtained as 5.18 min and 1.52 min, respectively. Cr(VI) adsorption by AC and AC/CoFe₂O₄ magnetic composite was spontaneous and exothermic. In general, our study showed that the composition of CoFe₂O₄ magnetic nanoparticles with AC can increase the adsorption capacity of AC from 36mg/L to 70mg/L.     

Removal of atrazine by photoelectrocatalytic process under sunlight using WN-codoped TiO<Subscript>2</Subscript> photoanode

The present study was focused on the degradation of Atrazine (ATZ) and major by-products (DEA, DIA, DEDIA and ATZ-OH) from water by photoelectrocatalytic (PEC) oxidation process under solar light. The undoped TiO₂, sub-stoichiometric TiO₂ (TiO_2?x) and codoped TiO₂ (TiO₂:WN) photoanodes were prepared by means of a radio frequency magnetron sputtering (RF-MS) deposition process. The X-ray photoelectron spectra (XPS) analysis shows that the N and W atoms were incorporated into the O and Ti lattice sites of TiO₂ respectively (case of TiO₂:WN film), while the XPS measurements of the TiO_2?x films composition was determined to be TiO_1.9. The UV–Vis transmittance spectra shows that in the case of the TiO₂:WN films, the presence of nitrogen and tungsten improve the optical response of TiO₂ under visible range compare to the presence of oxygen vacancies in to the TiO_2?x films. The experimental results under solar light with an initial concentration of ATZ (100 µg L^?1) show that after 180 min of treatment, the degradation of ATZ were 34.98%, 68.57% and 94.33% using TiO₂, TiO_2?x and TiO₂:WN photoanodes, respectively. These results of ATZ degradation proved that TiO₂:WN photoanode was more photoactive under solar light. The evolution by-products of ATZ under sunlight show that the principal mechanism of ATZ degradation was the oxidation of alkyl side chain and dealkylation.

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