柠檬酸改性Bi2O3光催化材料性能的研究

以Bi（NO3）3溶液为原料,浓氨水为矿化剂,在柠檬酸掺杂量为1％-3％（质量分数）的条件下制备了纳米Bi2O3粉体。以样品对水中罗丹明B的光催化降解性能为评价指标,对样品的光催化性能进行了评价。研究结果表明：采用水热合成法制备的柠檬酸改性纳米Bi2O3粉体光催化降解水中罗丹明B的反应为表观零级反应。当柠檬酸的掺杂量为1．5％时,样品的光催化性能最优,继续增加掺杂量,样品光催化性能有所下降。紫外光条件下样品的光催化性能优于日光条件下。     

Activation of glassy carbon electrodes by photocatalytic pretreatment

This paper describes a simple and rapid photocatalytic pretreatment procedure that removes contaminants from glassy carbon (GC) surfaces. The effectiveness of TiO₂ mediated photocatalytic pretreatment procedure was compared to commonly used alumina polishing procedure. Cyclic voltammetric and chronocoulometric measurements were carried out to assess the changes in electrode reactivity by using four redox systems. Electrochemical measurements obtained on photocatalytically treated GC electrodes showed a more active surface relative to polished GC. In cyclic voltammograms of epinephrine, Fe(CN)₆^3−/4− and ferrocene redox systems, higher oxidation and reduction currents were observed. The heterogeneous electron transfer rate constants (k^o) were calculated for Fe(CN)₆^3−/4− and ferrocene which were greater for photocatalytic pretreatment. Chronocoulometry was performed in order to find the amount of adsorbed methylene blue onto the electrode and was calculated as 0.34 pmol cm⁻² for photocatalytically pretreated GC. The proposed photocatalytic GC electrode cleansing and activating pretreatment procedure was more effective than classical alumina polishing.     

Effects of ITO thin films on microstructural and photocatalytic properties of layered TiO2/ITO films prepared via an extended deposition period

This study elucidates how indium tin oxide (ITO) thin film affects the microstructural and photocatalytic properties of layered TiO₂/ITO films prepared by DC magnetron sputtering. Two ITO substrates, as-received ITO (aITO) and in situ sputtered ITO (sITO), are adopted herein. Photocatalytic measurements of methylene blue and dimethyl sulfoxide indicate that the layered TiO₂/sITO film has greater photocatalytic oxidation than the TiO₂/aITO catalyst. According to photoelectrochemical tests, the latter exhibits a completely opposite activity to that of the former. Secondary ion mass spectrometry elemental depth profiles reveal that tin atoms in the sITO film really permeate into the growing TiO₂ film and promote the formation of the crystalline Ti_1−xSn_xO₂ layer. Additionally, cross-sectional transmission electron microscopy images and the selective area diffraction patterns show the difference between the diffusion of tin in the two catalysts. The photocatalytic oxidation capability is further enhanced in the layered TiO₂/sITO film because of an increase in the bandgap energy and a positive shift in the Fermi level energy of the Ti_1−xSn_xO₂ layer. Conversely, tin diffusion is limited in the aITO substrate under controlled conditions, in such a manner that a Schottky barrier can form at the TiO₂/aITO interface. Therefore, photogenerated electrons can be efficiently transferred from the overlaid TiO₂ film to the aITO substrate, producing a remarkable photocurrent density under UV illumination. Microstructural measurements reveal that the growth of the reactive {0 0 1} facets and columnar porous structure are favored by the synergetic effect of ITO substrate and an extended period of deposition. Accordingly, the photocatalytic capabilities are further raised.     

抗菌薄膜的最新研究进展

介绍了抗菌薄膜的抗菌机理。综述了抗菌薄膜的种类和最新研究进展。提出了抗菌薄膜研究的发展趋势,即无机抗菌薄膜以纳米复合型抗菌薄膜为主要的发展趋势;天然抗菌薄膜以壳聚糖抗菌薄膜为主要的发展方向;高分子抗菌薄膜以含吡啶基团的聚合物抗菌薄膜为拓展方向;光催化型无机抗菌薄膜以纳米TiO2复合抗菌薄膜为主要的拓展趋势。     

Effect of TiO2 thin film thickness and specific surface area by low-pressure metal–organic chemical vapor deposition on photocatalytic activities

TiO₂ photocatalyst films having an anatase crystal structure with different thickness were prepared by the low-pressure metal–organic chemical vapor deposition (LPMOCVD) to examine the effect of growth conditions on photocatalytic activity. Film thickness was linearly proportional to the deposition time. Structure of the film was strongly dependent on the deposition time. In early stage of deposition, fine particles deposit on the substrate. As increasing the deposition time, crystal orientation is gradually selected following the Kolmogorov model and c-axis oriented columnar crystals become dominant. The photocatalytic activity strongly depends on the film deposition time (or film thickness) in nonlinear way. The optimum thickness of TiO₂ catalyst film grown by LPMOCVD may locate between 3 and 5 μm.     

Bi12TiO20 synthesized directly from bismuth (III) nitrate pentahydrate and titanium glycolate and its activity

Pure phase of sillenite structure, Bi₁₂TiO₂₀, was directly synthesized using stoichiometric bismuth (III) nitrate pentahydrate and titanium glycolate by co-precipitation. The influence of pH on the structure of Bi₁₂TiO₂₀ was studied in the pH range of 3–10. The sillenite structure was characterized using XRD and FTIR. The photo-degradation reaction of 4-nitrophenol (4-NP) was used to study photocatalytic activity of Bi₁₂TiO₂₀ as a function of the preparation pH. The rate of decomposition was followed by UV-vis and TOC. The beginning concentration of 4-NP, 44 ppm, decreased to less than 1 ppm within 30 min for all prepared catalysts. It was found that the decomposition rate constant of Bi₁₂TiO₂₀ is six times higher than those of either TiO₂ or Bi₂O₃ under the same conditions.     

Photocatalytic degradation kinetics of di- and tri-substituted phenolic compounds in aqueous solution by TiO2/UV

In this study, photocatalytic degradation of 2,4,6-trimethylphenol (TMP), 2,4,6-trichlorophenol (TCP), 2,4,6-tribromophenol (TBP), 2,4-dimethylphenol (DMP), 2,4-dichlorophenol (DCP) and 2,4-dibromophenol (DBP) has been studied by TiO₂/UV. Although degraded phenolic compound concentration increased by increasing initial concentration photocatalytic decomposition rates of di- and tri-substituted phenols at 0.1–0.5 mM initial concentrations decreased when the initial concentration increased. The fastest degradation observed for TCP and the slowest for TMP. Photodegradation kinetics of the compounds has been explained in terms of Langmuir–Hinshelwood kinetics model. Degradation rate constants have been observed to be extremely depended on electronegativity of the substituents on phenolic ring. Degradation rate constant and adsorption equilibrium constant of TCP were calculated as k 0.0083 mM min⁻¹ and K 9.03 mM⁻¹. For TBP and TMP the values of k and K were obtained as 0.0040 mM min⁻¹, 19.20 mM⁻¹, and 0.0017 mM min⁻¹, 51.68 mM⁻¹, respectively. Degradation rate constant of DBP was similar as DCP (0.0029 mM min⁻¹ for DBP and 0.0031 mM min⁻¹ for DCP) whereas adsorption equilibrium constants differed (48.40 mM⁻¹ for DBP and 30.52 mM⁻¹ for DCP). K and k of DMP found as 83.68 mM⁻¹ and 0.0019 mM min⁻¹, respectively. The adsorption equilibrium constants in the dark were ranged between 1.11 and 3.28 mM⁻¹ which are lower than those obtained in kinetics. Adsorption constants have inversely proportion with degradation rate constants for all phenolic compounds studied.     

Fabrication and characterization of Ag–TiO2 multiphase nanocomposite thin films with enhanced photocatalytic activity

Ag–TiO₂ multiphase nanocomposite thin films were prepared on quartz substrates by the liquid phase deposition (LPD) method from a mixed aqueous solution of ammonium hexafluouotitanate, silver nitrate and boric acid under ambient temperature and atmosphere followed by calcination at 500 °C for 1 h. The grain growth of anatase was depressed upon Ag⁺ doping. However, silver ions not only promoted (or catalyzed) the formation of brookite phase but also reduced the phase transformation temperature of anatase to rutile. With increasing AgNO₃ concentration, the transmittance and band gap of the composite thin films decreased; however, the intensity of surface plasmon absorption (SPA) peaks increased and their peak position shifted to a longer wavelength range. When AgNO₃ concentration was higher than 0.03 M, the prepared samples consisted of anatase, brookite, rutile and metal silver nanocrystal particles, and their grain size ranges were 5–30 nm. The photocatalytic activity of the Ag–TiO₂ multiphase nanocrystal composite thin films prepared by this method exceeded that of pure TiO₂ thin films by a factor of more than 6.3 when AgNO₃ concentration was kept in the range of 0.03–0.05. This was attributed to the fact that there were many hetero-junctions, such as anatase/rutile, anatase/brookite, Ag/anatase, Ag/rutile and so on, existed in the Ag–TiO₂ multiphase nanocomposite films.     

Evaluation of humic acid photocatalytic degradation by UV–vis and fluorescence spectroscopy

Photodegradation of humic substances causes drastic changes in the UV–vis absorption and fluorescence properties of humic acids. In this study it is intended to fulfill the lack of knowledge about the spectral changes of humic acids during photocatalytic oxidation processes and elucidate the effects observed on the molecular size distribution of humic acid focusing on their analysis by UV–vis and fluorescence spectroscopy.

As confirmed by the spectroscopic evaluation of the molecular size distribution data, photocatalytic degradation of humic acid leads to the formation of lower molecular size (small fractions) and higher UV absorbing compounds. For fractions less than 10 kDa, UV₂₅₄ absorbing moieties in treated humic acid samples become higher than that of raw humic acid designating the generation of new species during photocatalysis. UV–vis spectroscopic changes were also evaluated by the parameters relating to the concomitant removal of the total organic carbon as well as by the ratios using absorption values at discrete wavelengths. Moreover, the fluorescence spectra of treated humic acid samples show decreasing intensity profiles with increasing photocatalytic irradiation time.     

纳米ZnO的制备及其光催化降解酸性红B

以Zn（acac）2·H2O为单源前驱体,用水热法成功地制备了纳米ZnO,利用X-射线衍射、扫描电子显微镜、透射电子显微镜等手段对样品进行了表征。对自制的纳米ZnO进行了光催化活性研究,结果表明：纳米ZnO对200～380nm波长范围的光和在可见光范围内都有较强的吸收作用。利用纳米ZnO作为光催化剂对有机染料溶液进行了降解实验,发现在太阳光照射3h后,对酸性红B的降解率可达到100%。