Fabrication and photoelectrocatalytic performance of C3N4-modified Ti/PbO2 anode with surface hydrophobicity

Journal of Solid State Electrochemistry - Reasonable hydrophobic anode is deemed to be a promising electrode for photoelectrocatalytic degradation of wastewater. In this study, the C3N4-modified...     

自支撑黑色TiO_2圆球的制备及其光催化性能的研究

为探索自支撑黑色Ti O2在可见光下降解有机污染物的催化性能,以粒径为385 nm的单分散白色Ti O2圆球为前驱体,再经H2氛500℃处理得到形貌尺寸未有明显改变的黑色Ti O2圆球。XRD和Raman结果表明黑色和白色Ti O2圆球的晶型为锐钛矿相;与白色Ti O2圆球相比,黑色Ti O2圆球的比表面积增大但是其带隙宽度降低为2.72 e V;黑色、白色Ti O2圆球和P25在可见光照下催化降解MB结果表明,黑色Ti O2圆球具有较好的催化活性,循环使用10次后,其催化活性没有明显衰减。     

Adsorption and photoelectrocatalytic characteristics of organics on TiO2 nanotube arrays

The adsorption and photoelectrocatalytic characteristics of four different kinds of organic compounds (d-fructose, glutamic acid, fumaric acid, and nicotinic acid) on TiO₂ nanotube arrays (TNAs) were investigated using a thin-layer cell, wherein the compounds were rapidly and exhaustively oxidized. The photogenerated current–time (I _ph–t) profiles were found to be related to the adsorption, the degradation rate, and the reaction mechanism. The relationship between the initial organic compounds concentrations and photocurrent peaks (I _0ph) fit the Langmuir type adsorption model well, thereby confirming that the adsorption of organic compounds on TNAs was via monolayer adsorption. The adsorption equilibrium constant was obtained from the Langmuir equation. The results indicate that the adsorption performance of the organic compounds on TNAs were in the following order: nicotinic acid < d-fructose < glutamic acid < fumaric acid. The degradation of organic compounds on TNAs was classified as either easy or difficult based on the time of complete mineralization (t _end) of the organic samples under an equal holes consumption; the degree of degradation were as follows: fumaric acid < d-fructose < glutamic acid < nicotinic acid. The photoelectrocatalytic characteristics of the organic compounds on TNAs were also discussed by analyzing the changes in the I _ph –t profiles.     

Compaction of TiO2 suspension utilizing hydrophilic/hydrophobic transition of cationic thermosensitive polymers

Compaction of TiO2 suspended particles utilizing the hydrophilic/hydrophobic transition of a cationic thermosensitive copolymer of N-isopropylacrylamide (NIPAM) and N-dimethylaminopropylacrylamide (DMAPAA) was examined. The surface of suspended TiO2 particles were sufficiently covered with the adsorbed polymer molecules at room temperature, and the suspension was subsequently heated above the transition temperature of the polymer. The thrusting motion of a plunger was used in order to provide an adequate mechanical force to compact the TiO2 suspended particles. The transition temperature was dependent on the DMAPAA content in the copolymer and the pH of the suspension. The transition temperature increased with increasing DMAPAA content and decreased with increasing pH. While suspended TiO2 particles were not compacted with poly(NIPAM), hard compacted sludge was readily obtained for cationic copolymer even if the content of DMAPAA groups was as low as 0.23 mol%. Furthermore, residual polymer molecules in the supernatant were not detected even if the polymer dosage was increased. These findings were attributed to the hydrophobic interaction of thermosensitive copolymer molecules adsorbed on TiO2 particles.     

Thermo‐ and pH‐sensitive triblock copolymers with tunable hydrophilic/hydrophobic properties

Polymers consisting of poly(acrylic acid) (PAA) and statistical poly[(acrylic acid)‐co‐(tert‐butylacrylate)] (P(AA‐co‐tBA)), attached to both extremities of Jeffamine® (D series based on a poly(propylene oxide) (PPO) with one amine function at each end) using atom transfer radical polymerization (ATRP) are presented in this article. An original bifunctional amide‐based macroinitiator was first elaborated from Jeffamine®. tBA polymerization was subsequently initiated from this macroinitiator. This polymerization occurs in a well‐controlled manner leading to narrow molecular weights distribution. Amphiphilic copolymers were finally obtained after complete or partial hydrolysis of the PtBA blocks into PAA. The control of the partial hydrolysis of tBA units, conducted in a concentrated HCl/tetrahydrofuran mixture, is demonstrated. The properties of the triblock copolymers were preliminary investigated in aqueous solution by absorbance, DLS measurements and SEC/MALS/DV/DRI analysis as a function of temperature and pH modifications, providing evidences of thermo‐ and pH‐sensitive self‐assembly of the copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2606–2616     

Fabrication of hydrophobic zeolites using triethoxyfluorosilane and their application as supports for TiO(2) photocatalysts

Hydrophobically modified Y-zeolites were prepared by simple modification with triethoxyfluorosilane (TEFS). These zeolites, used as supports, enhanced the efficiency of deposited TiO(2) for the photocatalytic degradation of organics diluted in water.     

Efficient photoelectrocatalytic activity of TiO2/Ti anode fabricated by metalorganic chemical vapor deposition (MOCVD)

Nanosized TiO₂/Ti photoanodes fabricated by metalorganic chemical vapor deposition (MOCVD) under different deposition temperatures were characterized and applied to the photoelectrocatalytic degradation of model pollutant of phenol. The anode prepared at 773 K was verified in anatase phase with a size about 60 nm and achieved the best photoelectrocatalytic activity, where IPCE could reach as high as 89% and the photoconversion efficiency peaked at 8.4%. The photoelectrocatalytic degradation of phenol was found well fit a pseudo-first-order kinetics, and kept stable performance in five continuous runs, confirming potential application of the electrode prepared by MOCVD for organic pollutants abatement.     

Fabrication of TiO2/Ti nanotube electrode and the photoelectrochemical behaviors in NaCl solutions

Titanium oxide nanotube electrodes were successfully prepared by anodic oxidation on pure Ti sheets in 0.5 wt.% NH₄F + 1 wt.% (NH₄)₂SO₄ + 90 wt.% glycerol mixed solutions. Nanotubes with diameter 40–60 nm and length 7.4 μm were observed by field emission scanning electron microscope. The electrochemical and photoelectrochemical characteristics of TiO₂ nanotube electrode were investigated using linear polarization and electrochemical impedance spectroscopy techniques. The open-circuit potential dropped markedly under irradiation and with the increase of Cl⁻ concentrations. A saturated photocurrent of approximately 1.3 mA cm⁻² was observed under 10-W low-mercury lamp irradiation in 0.1 M NaCl solution, which was much higher than film electrode. Meanwhile, the highest photocurrent in NaCl solution implied that the photogenerated holes preferred to combine with Cl⁻. Thus, a significant synergetic effect on active chlorine production was observed in photoelectrocatalytic processes. Furthermore, the generation efficiency for active chlorine was about two times that using TiO₂/Ti film electrode by sol–gel method. Finally, the effects of initial pH and Cl⁻ concentration were also discussed.     

Immunoactivity of polymer microspheres with their hydrophilic/hydrophobic heterogeneous surface sensitized with an antibody

Styrene/2-hydroxyethyl methacrylate polymer microspheres consisting of various polymer compositions were produced by emulsifier-free seeded emulsion polymerization technique. Using these microspheres, which should have hydrophilic/hydrophobic heterogeneous surface, the effects of surface hydrophilicity on the main, fundamental requirements for an immunomicrosphere — high colloidal stability, sensitive immunologic agglutinability and insensitive non-specific agglutinability — were studied in detail. There was a region of the surface hydrophilicity that satisfied the three requirements simultaneously.Part CII of the series Studies on Suspension and Emulsion.     

β-PbO2/Sb-SnO2/Ti电极的苯酚电催化性能研究

采用刷涂热解和电镀制得了β-PbO₂/Sb-SnO₂/Ti电极. 采用X射线衍射（X-ray Diffraction,XRD）和扫描电镜（Scanning Electron Microscope,SEM）进行分析与观察,Sb-SnO₂中间层抑制PbF₂的生成,NaF促进二氧化铅晶粒的成型与分散,消除了β-PbO₂聚团. 据谢乐公式（Scherrer）计算晶粒尺寸为25.2 nm,电极表面结晶度高达100%. 极化测试显示,β-PbO₂/Sb-SnO₂/Ti电极扩散段电位区、析氧电位和Tafel斜率分别为1.85 ~ 2.15 V、2.08 V和0.84,优于β-PbO₂/Ti电极的1.40 ~ 1.80 V、1.75 V和0.36. 使用β-PbO₂/Sb-SnO₂/Ti、β-PbO₂/Ti电极在9 mA·cm^-2电流密度对苯酚模拟废水处理240 min,前者COD（Chemical Oxygen Demand）去除率、电流效率（Instant Current Efficiency）高达90.1%和63.28%,优于后者66.9%和44.96%. 寿命测试表明,β-PbO₂/Sb-SnO₂/Ti电极与β-PbO₂/Ti电极相比延长10倍,工业寿命可达8.6a,有较高的工程应用价值.     

Ternary BiOBr/TiO2/Ti3C2Tx MXene nanocomposites with heterojunction structure and improved photocatalysis performance

The rational design and construction of heterojunction structure is an effective strategy to improve the photocatalytic performance. Herein, a series of BiOBr nanosheets-immobilized TiO₂/Ti₃C₂T_x MXene hybrid materials with heterojunction structure were synthesized by a facial one-step hydrothermal method. The ternary composites show outstanding performance as photocatalysts for the degradation of rhodamine B due to the optimized synergetic effects of BiOBr, TiO₂ and Ti₃C₂T_x. The improved photocatalytic performance is remarkably attributed to the construction of a heterojunction between TiO₂ and BiOBr due to their well-matching of energy band position, which can enhance the absorption for visible light and promote the transfer of photo-generated charge carriers. Moreover, Ti₃C₂T_x acts as an electron trap to further accelerate the separation of photo-generated electrons and holes.     

负载型混晶纳米TiO_2/硅藻土复合材料的制备及其光催化性能

选用市售硅藻土作为载体,采用液相沉积法制备了负载型混晶纳米TiO2/硅藻土复合材料;采用扫描电镜、X射线衍射仪及红外光谱仪分析了复合材料的表面形貌和晶体结构;基于甲醛光催化降解实验考察了不同组成的负载型TiO2/硅藻土复合材料的光催化性能.结果表明,TiO2负载量为33.3%(TiO2与硅藻土的质量比为1∶2)的复合材料对甲醛光催化降解具有最佳催化活性.     

Preparation of TiO2/ITO film electrode by AP-MOCVD for photoelectrocatalytic application

Titanium dioxide (TiO2 ) thin films were grown onto Indium tin oxide (ITO) glass under atmospheric pressure by chemical vapor deposition (AP-MOCVD) using titanium tetraisopropoxide astitanium precursor. The as-prepared TiO2 /ITO films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and photoelectrochemical measurements. Their photocatalytic (PC) and photoelectrocatalytic (PEC) activities were evaluated based on the results of methyl orange dye (MO) degradation experiments in aqueous solution. The difference between the front side (EE, electrolyte/electrode interface) and the back side (SE, substrate/electrode interface) illumination was evaluated in both photocurrent and MO degradation experiments. The effect of the film thickness on degradation rate by PEC under the two illumination directions was also studied. Stability of TiO2 /ITO film electrode was investigated in repetitive degradation experiments. Overall, the TiO2 /ITO film with thickness ranging from 321 to1440 nm deposited by MOCVD method is an effective photoelectrode for MO degradation under SE illumination in PEC reaction system.     

Open circuit potential measurements with Ti/TiO2 electrodes

The open circuit potential (OCP) vs pH response of Ti/TiO₂ electrodes prepared by thermal and electrochemical oxidation of metallic titanium was measured in KNO₃ aqueous solutions in order to establish whether the slopes of the OCP-pH curves can be used as a measure of the variation of surface potential (ψ_o) of TiO₂ with the pH of the aqueous solution. For comparison purposes, ψ_o—pH slopes were also evaluated from surface charge-pH data obtained by acid-base potentiometric titrations of TiO₂ dispersions.Ti/TiO₂ electrodes showed a linear OCP-pH response in the range of ph 5–10 with slopes of −0.039 ± 0.005 V ph⁻¹. The OCP-pH dependence of Ti/TiO₂ electrodes was lower than that predicted thermodynamically. According to the triple-layer model, used to describe the oxide/aqueous solution interface, the OCP-pH slopes obtained for Ti/TiO₂ electrodes cannot be identified with the variation of ψ_o with the pH. Calculations with this model indicated that neither the single nor the double extrapolation methods used to evaluate the intrinsic ionization constant of oxide surface sites render realistic values of these parameters for the TiO₂ surface.The analysis of surface charge—pH data and the use of the triple-layer model to predict experimental values indicated that the ψ_o—pH slopes of TiO₂ surfaces must be greater (in absolute magnitude) than 0.041 V pH⁻¹.     

Influence of particle size on the photoactivity of Ti/TiO2 thin film electrodes,and enhanced photoelectrocatalytic degradation of indigo carmine dye

Photoanodes based on Ti/TiO₂ thin films were prepared by the sol–gel method, using either tetraisopropoxide (Ti(OPri)₄) or modified tetraisopropoxide, producing electrodes with different sized nanoparticle coatings, termed nanoporous (20 nm) or nanoparticulated (10 nm) electrodes. The anatase form dominated the composition of the nanoparticulated electrode, which presented a higher surface area, a flat band potential shift of ?160 mV and a 50% improvement in photoactivity, compared to the nanoporous electrode. 100% color removal, and 75% mineralization, of indigo carmine dye were achieved after 15 min of photoelectrocatalytic treatment using a nanoparticulated Ti/TiO₂ electrode operated at a current density of 0.4 mA cm^?2. Our findings indicate that the use of nanoparticulated electrodes, under UV irradiation and with controlled current density, is an efficient alternative for the removal of food dye contaminants during wastewater treatment.     

Fabrication of TiO2 using L-lysine-based organogelators as organic templates: control of the nanostructures

Using uncharged or negatively charged L-lysine-based organogelators as templates, the nanostructures of TiO2 are controllable.     

Effect of hydrophobic/hydrophilic characteristics of magnetic microspheres on the immobilization of BSA

Core-shell magnetic poly(styrene-acrylamide-acrylic acid) microspheres with carboxyl groups were successfully synthesized via dispersion copolymerization in the presence of nano-particle of Fe(3)O(4). The microspheres were characterized by FTIR spectra. They were used as carrier to immobilize bovine serum albumin (BSA). To investigate the effect of the microsphere surface properties on the immobilization of BSA, a series of microspheres with different hydrophobic/hydrophilic surface characteristics were prepared by adjusting molar percentages of monomers. The results showed that microspheres with different hydrophobicities/hydrophilicities had different immobilized ratios of BSA. In comparison with microspheres having hydrophilic characteristics those with hydrophobic characteristics had a much higher immobilized ratio. The possible reasons for these observations are discussed. In addition, ester activation and coupling times were optimized with respect to immobilized ratio.     

Stabilization of O/W emulsion with hydrophilic/hydrophobic clay particles

In this study, a stabilizing behavior of clay in a 40/60 w/w oil-in-water (O/W) emulsion is investigated by macro- and microscopic morphological observations, rheology, and X-ray diffraction measurements. Hydrophilic and hydrophobic clays (Montmorillonites) are tested for stabilization of emulsion. When hydrophilic clay showing interfacial localization is added to the emulsion, emulsion is not stable to phase separation (creaming). With hydrophobic clay, the emulsion shows phase inversion to water-in-oil (W/O) emulsion due to the increase in oil viscosity which results in phase separation of sedimentation. On the other hand, with the mixture of hydrophilic and hydrophobic clays, the emulsion shows a synergistic macroscopic and microscopic stabilization due to the formation of composite structure at the interface by hydrophilic and hydrophobic clays.