Properties of sol-gel SnO2/TiO2 electrodes and their photoelectrocatalytic activities under UV and visible light illumination

A visible light active binary SnO₂-TiO₂ composite was successfully prepared by a sol-gel method and deposited on Ti sheet as a photoanode to degrade orange II dye. Titanium and SnO₂ can promote the development of rutile phase of TiO₂ and inhibit the formation of anatase phase of TiO₂. Formation of SnO₂ crystalline is insignificant even when the calcination temperature increases to 700 °C. Heterogenized interface between SnO₂ and TiO₂ inhibits growth of TiO₂ linkage and leads to the particle-filled surface morphology of SnO₂-containing films. The carbonaceous, Ti-O-C bonds and Ti³⁺ species are likely to account for the photoabsorption and photoelectrocatalytic (PEC) activity under visible light illumination. The electrode with 30% SnO₂ exhibits higher photocurrent when compared with those in the region of 0-50%. The 600 °C-calcined SnO₂-TiO₂ electrode indicates higher activity when compared with those at 400, 500, 700 and 800 °C. PEC degradation of orange II follows the Langmuir-Hinshelwood model and takes place much effectively in a solution of pH 3.0 than those in pH 7.0 and pH 11.0.     

Efficient decomposition of organic compounds with FeTiO3/TiO2 heterojunction under visible light irradiation

FeTiO₃/TiO₂, a new heterojunction-type photocatalyst working at visible light, was prepared by a simple sol–gel method. Not only did FeTiO₃/TiO₂ exhibit greatly enhanced photocatalytic activity in decomposing 2-propanol in gas phase and 4-chlorophenol in aqueous solution, but also it induced efficient mineralization of 2-propanol under visible light irradiation (λ ≥ 420 nm). Furthermore, it showed a good photochemical stability in repeated photocatalytic applications. FeTiO₃ showed a profound absorption over the entire visible range, and its valence band (VB) position is close to that of TiO₂. The unusually high photocatalytic efficiency of the FeTiO₃/TiO₂ composite was therefore deduced to be caused by hole transfer between the VB of FeTiO₃ and TiO₂.     

Preparation and characterization of TiO2/Ti film electrodes by anodization at low voltage for photoelectrocatalytic application

Multiporous TiO₂/Ti film electrodes were prepared by different anodic oxidation processes at low voltage, in which the micro-structured TiO₂ thick films were prepared in H₂SO₄–H₂O₂–H₃PO₄–HF solution for 2 h and the nano-structured TiO₂ thin films were prepared in H₃PO₄–HF solution for 30 min with post-calcination. Both types of TiO₂/Ti films were characterized by scanning electron microscopy and X-ray diffraction analysis. The photocatalytic (PC) and photoelectrocatalytic (PEC) reactivity of the TiO₂/Ti electrodes were evaluated in terms of bisphenol A (BPA) degradation in aqueous solution. The experimental results demonstrated that the nano-structured TiO₂/Ti thin-film electrodes had higher reactivity in the BPA degradation reaction. The PEC degradation of BPA was further studied using different cathodes, either a reticulated vitreous carbon (RVC) electrode or a platinum (Pt) electrode. The experimental results confirmed that the efficiency of BPA degradation could be significantly enhanced in the TiO₂/Ti–RVC reaction system due to the generation of H₂O₂ on the RVC cathode. It is believed that such a H₂O₂-assisted TiO₂ PEC oxidation process may have good potential for water and wastewater treatment.     

Visible light-induced photocatalytic activity of delafossite AgMO2 (M = Al, Ga, In) prepared via a hydrothermal method

Delafossite-structured oxides AgMO₂ (M = Al, Ga, In) were successfully synthesized using fluoro(ethylene-propylene) (FEP) pouch via a facile hydrothermal method. The obtained samples were characterized by X-ray diffraction (XRD), BET surface area measurement, UV–vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the as-prepared samples was evaluated by the degradation of rhodamine B (RhB) and methyl orange (MO) under visible light irradiation. All three samples showed photocatalytic activity for RhB and MO degradation under visible light irradiations and their photocatalytic activity followed the order of AgInO₂ > AgGaO₂ > AgAlO₂. The relative high photocatalytic activity of AgInO₂ can be attributed to its high quantity of the surface hydroxyl groups. The photocatalytic mechanism of AgInO₂ was proposed and its stability was also investigated.     

Heterostructure-based 3D-CdS/TiO2 nanotubes/Ti: Photoelectrochemical performances and interface simulation investigation

Heterojunction can effectively improve the charge separation efficiency and facilitate electron transfer, producing a strong photoelectric signal. By using 3D-TiO₂ nanotubes/Ti foil as support, CdS–TiO₂ heterojunction electrodes with different CdS proportions were fabricated as photoelectrochemical (PEC) biosensor to respond the visible irradiation and improve the PEC performance of TiO₂ nanotubes. Density functional theory (DFT) simulation was conducted to clarify the PEC process of CdS–TiO₂NTs and revealed the important role of CdS in enhancing electron–hole separation on TiO₂ nanotubes. Owing to the 3D tubular structure of the support, 2 mM CdS–TiO₂ nanotubes/Ti PEC electrode exhibited low detection limit of 0.27 μM and good sensitivity of 328.87 μA mM^?1 cm^?2 for glucose in the range of 2–9 μM under visible illumination. The fabricated CdS–TiO₂ nanotubes/Ti biosensor also showed high selectivity and good stability, which indicated a new candidate for biosensors.     

Synthesis and characterization of polythiophene/titanium dioxide composites

Polythiophene/titanium dioxide (PT/TiO₂) composites were prepared by the in situ chemical oxidative polymerization method. The resulting PT/TiO₂ composites were characterized by Fourier transform infrared (FT-IR) spectroscopy, ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and field emission scanning electron microscopy (SEM). UV–Vis diffuse reflectance spectra measurements show that the PT/TiO₂ composites can adsorb light of wavelengths ranging from 200 nm to 800 nm. The PT/TiO₂ composites showed good adsorption properties and were more efficient in removing dye from solution than pure PT and pure TiO₂. The PT/TiO₂ composites exhibited photocatalytic activities to some extent under UV light illumination.     

Self-assembly of BixTi1−xO2 visible photocatalyst with core–shell structure and enhanced activity

Mesoporous Bi_xTi_1−xO₂ spheres with core–shell chamber were prepared by alcoholysis under solvothermal conditions. The cross-condensation between Ti–OH and Bi–OH ensured complete incorporation of Bi-dopants into TiO₂ lattice, though Bi atom is much bigger than Ti. Meanwhile, the aggregation of titania building clusters into spheres and their subsequent reactions including dissolution and re-deposition processes lead to the hollow spheres with tunable interior structure. The Bi-doping induced strong spectral response in visible region owing to the formation of narrow intermediate energy band gaps. Meanwhile, multiple reflections within the sphere interior voids promoted the light absorbance. As a result, the as-prepared Bi_xTi_1−xO₂ spheres exhibited much higher activity than the undoped TiO₂, the Bi₂O₃/TiO₂ obtained by impregnating the TiO₂ with Bi(NO₃)₃ solution, and the Bi_xTi_1−xO₂ after being ground during photodegradation of p-chlorophenol under visible light irradiation. Meanwhile, the Bi_xTi_1−xO₂ could be used repetitively for 10 times owing to the high hydrothermal stability and the absence of Bi-leaching.     

Preparation of Ti/SnO2-Sb2O4 photoanode by electrodeposition and dip coating for PEC oxidations

Thin films of antimony-doped SnO₂ on titanium substrate with a doping range of 1.5-8 mol% were prepared by an electrodeposition and dip coating method. The prepared Ti/SnO₂-Sb₂O₄ thin films were tested as a photoanode in the photoelectrocatalytic(PEC) experiments to degrade phenol in aqueous solution in order to evaluate their PEC performance. The photocatalytic (PC), electrocatalytic (EC) and PEC activity of Ti/SnO₂-Sb₂O₄ thin films was compared in the degradation processes. And the effect of annealing temperature on their PEC activity was also investigated. The experimental results confirmed that the Sb-doped Ti/SnO₂ thin films enhanced the phenol degradation and the Ti/SnO₂-Sb₂O₄ film containing 6 mol% of Sb calcinated at 450 °C achieved the best performance for phenol degradation. The degradation experiments also demonstrated that the Ti/SnO₂-Sb₂O₄ film achieved faster degradation of phenol in the PEC process than in the PC and EC processes. Compared with Ti/TiO₂ and Ti/SnO₂ photoanodes, the Ti/SnO₂-Sb₂O₄ photoanode showed higher activity.     

Nb/N Co-Doped Layered Perovskite Sr2TiO4: Preparation and Enhanced Photocatalytic Degradation Tetracycline under Visible Light

Sr₂TiO₄ is a promising photocatalyst for antibiotic degradation in wastewater. The photocatalytic performance of pristine Sr₂TiO₄ is limited to its wide bandgap, especially under visible light. Doping is an effective strategy to enhance photocatalytic performance. In this work, Nb/N co-doped layered perovskite Sr₂TiO₄ (Sr₂TiO₄:N,Nb) with varying percentages (0–5 at%) of Nb were synthesized by sol-gel and calcination. Nb/N co-doping slightly expanded the unit cell of Sr₂TiO₄. Their photocatalytic performance towards antibiotic (tetracycline) was studied under visible light (λ > 420 nm). When Nb/(Nb + Ti) was 2 at%, Sr₂TiO₄:N,Nb(2%) shows optimal photocatalytic performance with the 99% degradation after 60 min visible light irradiation, which is higher than pristine Sr₂TiO₄ (40%). The enhancement in photocatalytic performance is attributed to improving light absorption, and photo-generated charges separation derived from Nb/N co-doping. Sr₂TiO₄:N,Nb(2%) shows good stability after five cycles photocatalytic degradation reaction. The capture experiments confirm that superoxide radical is the leading active species during the photocatalytic degradation process. Therefore, the Nb/N co-doping in this work could be used as an efficient strategy for perovskite-type semiconductor to realize visible light driving for wastewater treatment.     

Oxidation of CH4 over Pd supported on TiO2-doped SiO2: Effect of Ti(IV) loading and influence of SO2

Titania-modified silicas with different weight% of TiO₂ were prepared by sol–gel method and used as supports for Pd (1 wt%) catalysts. The obtained materials were tested in the oxidation of methane under lean conditions in absence and in presence of SO₂. Test reactions were consecutively performed in order to evaluate the thermal stability and poisoning reversibility. Increasing amounts of TiO₂ improved the catalytic activity, with an optimum of the performance for 10 wt% TiO₂ loading. Moreover, the titania-containing catalysts exhibited a superior tolerance towards SO₂ by either adding it to the reactants or feeding it as a pure pretreatment atmosphere at 350 °C. Catalysts were characterized by XPS, XRD, FT-IR and BET measurements. According to the structural and surface analyses, the mixed oxides contained Si–O–Ti linkages which were interpreted as being responsible for the enhanced intrinsic activity of supported PdO with respect to PdO on either pure SiO₂ or pure TiO₂. Moreover, the preferential interaction of the sulfur molecule with TiO₂ and the easy SO_x desorption from high surface area silica were the determining factors for the superior SO₂ tolerance of the TiO₂-doped catalysts.     

Preparation of short, robust and highly ordered TiO2 nanotube arrays and their applications as electrode

The short, robust and highly ordered TiO₂ nanotube arrays (TNAs) electrode was prepared by sonoelectrochemical anodization of titanium in HF–H₂O electrolyte solution (referred as short TNAs, STNAs). The self-organized arrays of titania nanotubes of approximately 12–65 nm in diameter and 75–280 nm in length can be synthesized at anodic voltage of 5–20 V. The electron transport process within the STNAs electrode was much favorable in comparison with that for the long TNAs electrode synthesized by conventional magnetic agitation technique (referred as long TNAs, LTNAs), as confirmed by the obviously enhanced photocurrent response of STNAs electrode either in 0.02 M Na₂SO₄ electrolyte solution or in different concentrations of glucose solution or under different intensities of UV illumination. To investigate their photoelectrochemical applications, degradation of tetracycline, a typical pharmaceutical and personal care products (PPCPs), was carried out using photoelectrocatalytic (PEC) means, comparing with electrochemical (EC) and photocatalytic (PC) processes. The kinetic constant of the PEC process of STNAs electrode was 3.17 times as high as its PC process. The color removal rate of tetracycline by STNAs electrode achieved 81% within 3 h, which was 21% higher than that for LTNAs electrode. In degrading tetracycline, 41% of TOC was mineralized using the STNAs electrode against 23% using LTNAs electrode under similar conditions. Such kind of titania nanotubes will have many potential applications in various areas as an outstanding photoelectrochemical material.     

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%.     

Synergistic effect of TiO2 and iron oxide supported on fluorocarbon films. Part 1: Effect of preparation parameters on photocatalytic degradation of organic pollutant at neutral pH

Iron oxide and TiO₂ were immobilized on modified polyvinyl fluoride films in a sequential process. Synergic effects of iron oxide and TiO₂ on the polymer film were observed during the heterogeneous degradation of hydroquinone (HQ) in the presence of H₂O₂ at pH close to neutrality and under simulated solar irradiation. Within the degradation period, little iron leaching (<0.5 mg/L) was observed.The surface of commercial polyvinyl fluoride (PVF) film was modified by TiO₂ under light inducing oxygen group (C–OH, CO, COOH) formation on the film surface. During this treatment, TiO₂ nanoparticles simultaneously bind to the film, leading to PVF^f–TiO₂. The possible mechanistic pathway for the TiO₂ deposition and the nature of the polymer–TiO₂ interaction are discussed. Furthermore PVF and PVF^f–TiO₂ were immersed in an aqueous solution for the deposition of iron oxide layer by hydrolysis of FeCl₃, leading to PVF–Fe oxide and to PVF^f–TiO₂–Fe oxide respectively.HQ degradation and mineralization mediated by PVF^f–TiO₂, PVF–Fe oxide and PVF^f–TiO₂–Fe oxide were investigated under different conditions. Remarkable synergistic effects were observed for PVF^f–TiO₂–Fe oxide possibly due to Fe(II) regeneration, accelerated by electron transfer from TiO₂ to the iron oxide under light.     

Nb2O5 as efficient and recyclable photocatalyst for indigo carmine degradation

Heterogeneous photocatalysis is a significant green technology for application in water purification. The application of Nb₂O₅ catalyst for the photodegradation of contaminants is few reported in the literature. Thus, the Nb₂O₅ catalyst was characterized by SEM, FTIR, surface area and charge surface density. This catalyst was applied to degrade indigo carmine dye, which was compared with degradation catalyzed by TiO₂ and ZnO. Almost 100% of dye degradation occurred at 20, 45 and 90 min for TiO₂, ZnO and Nb₂O₅, respectively. The effect of Nb₂O₅ catalyst concentration, pH and ionic strength (μ) was investigated. The Nb₂O₅ activity increased at 0.7 g/L and for higher catalyst concentrations the degradation was kept constant. Degradation of indigo carmine dye catalyzed by Nb₂O₅ was improved at pH < 4.0 and μ = 0.05 mol/L. TiO₂, ZnO and Nb₂O₅ were recovered and re-applied in other nine reaction cycles. While TiO₂ and ZnO have an abrupt loss of their catalytic activity, Nb₂O₅ maintained 85% of catalytic activity after 10 reaction cycles.     

ML-WO3/TiO2异质结的制备及其对罗丹明B的光催化降解

采用空间限域法制备了单层三氧化钨纳米片(ML-WO₃),然后将其与TiO₂复合得到ML-WO₃/TiO₂纳米材料,被用来在模拟太阳光下对罗丹明B进行光催化降解。ML-WO₃/TiO₂的组成和光学特性通过扫描电镜、透射电镜、高分辨透射电镜、X射线衍射、紫外-可见吸收光谱和光致发光光谱手段进行表征。结果证实,纳米ML-WO₃/TiO₂克服了纯TiO₂带隙较大的缺陷,在全波段太阳光表现出比ML-WO₃和TiO₂更强的吸收性能,ML-WO₃与TiO₂之间具有明显的协同效应。活性物种捕获实验表明.OH和.O_2^-自由基是RhB降解的主要活性物种。ML-WO₃和TiO₂之间构建的Z型异质结电荷转移路径能够保证光生载流子的高效分离和重组。在5次循环实验后ML-WO₃/TiO₂的光催化活性仍能接近80%,具有良好的光化学稳定性。通过高效液相色谱-质谱检测RhB的中间产物,推测了RhB可能的降解路径。     

Photoassisted mineralization of remazole red F3B over NiO/TiO2 and CdO/TiO2 nanoparticles under simulated sunlight

In this work, a series of titania-supported NiO and CdO materials were synthesized by a modified sol-gel process. The prepared photocatalysts were characterized by X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS), and transmission electron microscopy (TEM). The activities of titania-supported NiO and CdO photocatalysts for photocatalytic degradation of Remazole Red F3B (RR) dye, under simulated sunlight, were investigated. The photocatalytic mineralization of an RR dye solution over various NiO-x/TiO₂ and CdO-x/TiO₂ photocatalysts under simulated sunlight was investigated. It was worthy noticing that the photocatalytic activity of titania improved using the prepared catalysts. The prepared TiO₂, NiO-5/TiO₂, and CdO-2/TiO₂ photocatalysts exhibited higher photocatalytic activity under simulated sunlight than did commercial TiO₂. The prepared photocatalysts were stable after photocatalytic degradation of the dye. The observed photocatalytic mineralization of the dye was 51 and 71% over NiO-10/TiO₂ and CdO-2/TiO₂ after 180 min of irradiation, respectively. Juxtaposing a p-NiO-5/TiO₂ semiconductor provided a potential approach for decreasing charge recombination. The prepared photocatalystsNiO-5/TiO₂ and CdO-2/TiO₂ are promising composites for the solar detoxification of textile wastewater.     

A VOx/meso-TiO2 catalyst for methanol oxidation to dimethoxymethane

Mesoporous TiO₂ was prepared by simply controlling the hydrolysis of Ti(OBu)₄ with the help of acetic acid. The mesoporous TiO₂ had a well-crystallized anatase phase and a high surface area of 290 m² g⁻¹ with a pore size of about 4 nm. The anatase phase and the mesoporous structure were maintained in the VO_x/TiO₂ catalyst with a monolayer dispersion of V₂O₅, however, the surface area decreased to 126 m² g⁻¹. The catalyst was highly active and selective for methanol oxidation, giving about 55% conversion of methanol and 85% selectivity to dimethoxymethane at 423 K.     

Mechanisms of photocatalytic degradation of Victoria Blue R using nano-TiO2

The TiO₂-mediated photocatalysis process was used to successfully degrade dye pollutants. To better understand the mechanistic details of this TiO₂-assisted photodegradation of the Victoria Blue R (VBR) dye with UV irradiation, forty-four intermediates of the process were separated, identified and characterized by HPLC–PDA–ESI-MS (high performance liquid chromatography–photodiode array–electrospray ionization-mass spectrometry) technique in this study, and their evolution during the photocatalytic reaction is presented. The results indicated that the N-de-alkylation degradation of VBR dye took place in a stepwise manner to yield mono-, di-, tri-, tetra-, penta-, hexa-N-de-methylated and mono-N-de-ethylated VBR species, with N-hydroxyalkylated intermediates generated during the process. Moreover, the oxidative degradation yielded 4-diethylaminophenol, 4-diethylamino-4′-diethylaminobenzophenone, 4-(N,N-dimethylaminophenyl)-4′-(N′-ethylaminonaphthyl)ketone, 4-(N-ethylamino)naphthenol and their N-de-alkylated products. The reaction mechanisms of TiO₂/UV proposed in this study should be useful for future application of the technology to the degradation of dyes.     

An efficient and energy saving approach to photocatalytic degradation of opaque high-chroma methylene blue wastewater by electrocatalytic pre-oxidation

The opaque methylene blue (MB) dye wastewater hard to be degraded directly by photocatalytic (PC) oxidation was successfully decomposed by a new two-step process, in which electrocatalytic (EC) pre-oxidation was followed with photoelectric synergistic catalytic (PEC) oxidation. The SnO₂/TiO₂ NTs electrode was used as the anode, which simultaneously has superior EC and PC performance. In the pre-oxidation step, the opaque dye wastewater is decolorized by EC oxidation, and the wastewater becomes a light transmission system, which provides the necessary condition for PC oxidation. However, the individual EC oxidation will be of low current efficiency and high energy consumption for the decreasing of the pollutants concentration in wastewater. Thus, in second stage, the PC process was introduced, and the synergistic catalytic oxidation leads to high PEC oxidation efficiency, so that the complete mineralization of the MB dye wastewater was realized. The whole process is highly efficient and energy-saving, which opens a new avenue to degrade the high-chroma or opaque dye wastewater.     

Photocatalytic decolorization of rhodamine B by fluidized bed reactor with hollow ceramic ball photocatalyst

Photocatalytic degradation of organic contaminants in wastewater by TiO₂ has been introduced in both bench and pilot-scale applications in suspended state or immobilized state on supporting material. TiO₂ in suspended state gave less activity due to its coagency between particles. Recent advances in environmental photocatalysis have focused on enhancing the catalytic activity and improving the performance of photocatalytic reactors. This paper reports a preliminary design of a new immobilized TiO₂ photocatalyst and its photocatalytic fluidized bed reactor (PFBR) to apply photochemical degradation of a dye, Rhodamine B (RhB). But it was not easy to make a cost-effective and well activated immobilized TiO₂ particles. A kind of photocatalyst (named Photomedium), consisting of hollow ceramic balls coated with TiO₂-sol, which was capable of effective photodegradation of the dye, has been presented in this study. The photocatalytic oxidation of RhB was investigated by changing Photomedia concentrations, initial RhB concentrations, and UV intensity in PFBR This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.