纺锤形BiVO4微米管：低温离子熔盐合成及光催化性能

以Bi(NO₃)₃·5H₂O和NH₄VO₃为原料,以氯化胆碱和尿素组成的低温离子熔盐为反应介质,采用离子热合成法成功制备出了具有纺锤状外形的BiVO₄微米管。利用XRD,SEM,UV-Vis DRS,光催化测试等手段考察了BiVO₄颗粒的物相、形貌和光催化性能。结果表明,在离子熔盐环境下可以制备出结晶良好的BiVO₄纺锤形微米管,该BiVO₄微米管长10~15 μm,直径为1.5 μm左右,管壁厚约为200 nm。同时,研究了pH值对BiVO₄颗粒物相与形貌的影响,发现随着pH值的变化可分别合成出具有柱状、纺锤形微米管、柱状微米管和针柱状单斜相BiVO₄颗粒。光催化测试结果表明,这些单斜白钨矿BiVO₄颗粒在可见光范围都具有一定的光催化活性,其中纺锤状微米管对罗丹明B的降解效果最佳,可见光照射4.5 h后罗丹明B的降解率可达到93％。     

DFT calculations on the electronic structures of BiOX (X = F, Cl, Br, I) photocatalysts with and without semicore Bi 5d states

The electronic structures of BiOX (X = F, Cl, Br, I) photocatalysts have been calculated with and without Bi 5d states using the experimental lattice parameters, via the plane-wave pseudopotential method based on density functional theory (DFT). BiOF exhibits a direct band gap of 3.22 or 3.12 eV corresponding to the adoption of Bi 5d states or not. The indirect band gaps of BiOCl, BiOBr, and BiOI are 2.80, 2.36, and 1.75 eV, respectively, if calculated with Bi 5d states, whereas the absence of Bi 5d states reduces them to 2.59, 2.13, and 1.53 eV successively. The calculated gap characteristics and the falling trend of gap width with the increasing X atomic number agree with the experimental results, despite the common DFT underestimation of gap values. The shapes of valence-band tops and conduction-band bottoms are almost independent of the involvement of Bi 5d states. The indirect characteristic becomes more remarkable, and the conduction-band bottom flattens in the sequence of BiOCl, BiOBr, and BiOI. Both O 2p and X np (n = 2, 3, 4, and 5 for X = F, Cl, Br, and I, respectively) states dominate the valence bands, whereas Bi 6p states contribute the most to the conduction bands. With the growing X atomic number, the localized X np states shift closer toward the valence-band tops, and the valence and conduction bandwidths evolve in opposite trends. Atomic and bond populations have also been explored to elucidate the atomic interactions, along with the spatial distribution of orbital density.     

TiO2光催化氧化去除有机污染物的研究进展

本文综述了近年来TiO2光催化降解有机污染物的研究进展，讨论了各类 有机污染物光催化氧化反应的特点、影响反应速率的因素及光催化体系的改进。     

Role of Cl ions in photooxidation of propylene on TiO2 surface

The effect of Cl⁻ ions on photooxidation of propylene on TiO₂ semiconductor was investigated. Cl⁻/TiO₂ catalysts were prepared by annealing Degussa P25 TiO₂ in the gas flow of N₂ and Cl₂ under 100-400 °C. The photocatalytic oxidation of propylene was carried out in a continuous flow system, with the chromatograph to analyze the products on line. The experimental results showed that the activity of Cl⁻/TiO₂ catalysts increased as heat-treated temperature decreased. The activity of the sample heat-treated at 100 °C was about two times higher than that of pure TiO₂. Moreover, as to TiO₂, the main product of the propylene photocatalytic oxidation was CO₂, but with Cl⁻/TiO₂ catalysts, not only CO₂ but also trace CO was determined. The adsorbed species on TiO₂ surface before and after reaction were analyzed by X-ray photoelectron spectroscopy (XPS) and thermogravimetric/differential thermal analyses (TG-DTA) coupled to a mass spectrometer (MS). XPS analysis showed that there was Cl⁻ absorbed on the Cl⁻/TiO₂ surface, and the absorption amount of Cl⁻ decreased after the photooxidation reaction of propylene. TG-DTA-MS analysis confirmed chlorine absorbed on the surface of TiO₂ in the form of Cl⁻ ion. These results illuminated that absorbed Cl⁻ on the surface of TiO₂ formed a weak physical absorption on TiO₂ at low temperature, and subsequently participated in the photooxidation of propylene, finally removed from TiO₂ surface.     

Visible-Light Activities of Erbium Doped BiVO4 Photocatalysts

采用水热合成法,制备出Er掺杂的BiVO₄复合光催化剂,并采用XRD、SEM、XPS和紫外-可见漫反射光谱技术对其进行分析表征．通过可见光下降解水溶液中甲基橙分子来考察其光催化性能,结果显示掺杂组份以氧化物Er₂O₃形式存在于的复合光催化剂中;且掺杂复合光催化剂的可见光吸收和催化活性都比纯BiVO₄有所增强．     

Investigation into the effects of deposition parameters on TiO2 photocatalyst thin films by rf magnetron sputtering

Titanium dioxide (TiO₂) photocatalyst thin films were deposited on non-alkali glass substrates by radio frequency (rf) magnetron sputtering. The Taguchi method with orthogonal array, signal-to-noise ratio and analysis of variance were employed to study the performance characteristics. The experimental studies were conducted under different rf powers, sputtering pressures, O₂/(Ar+O₂) flow-rate ratios, and substrate temperatures. The deposited TiO₂ films were of the anatase phase with a (101) preferred orientation. We performed both photoinduced decomposition of methylene blue (MB) and photoinduced hydrophilicity under UV light illumination. With the optimized TiO₂ photocatalyst thin film deposition conditions, the water contact angle after 9 min UV illumination was approximately 5, the absorbance of MB was reduced to 0.2 for 240 min UV irradiation, and the deposition rate was 34.18 Å/min.     

Active and recyclable ordered mesoporous magnetic organometallic catalyst as high‐performance visible light photocatalyst for degradation of organic pollutants

A novel light‐active magnetic Pd complex as a photocatalyst was prepared through bonding organometallics to mesoporous silica channels formed on the surface of silica‐coated iron oxide nanoparticles. The nanocomposite (denoted as Fe₃O₄@SiO₂@m‐SiO₂@PDA‐Pd(0); PDA = 1,10‐phenanthroline‐2,9‐dicarbaldehyde) is more efficient and has higher photocatalytic capability in the degradation of 2,4‐dichlorophenol under visible light irradiation compared with virgin Pd complex (PDA‐Pd). This noteworthy photodegradation activity can be due to the high dispersion of Pd nanoparticles. High yield, low reaction time and non‐toxicity of the catalyst are the main merits of this protocol. Also magnetic separation is an environmentally friendly alternative method for the separation and recovery of the catalyst, since it minimizes the use of solvents and auxiliary materials, reduces operation time and minimizes catalyst loss by preventing mass loss and oxidation. The produced Pd catalyst was characterised using various techniques. Furthermore, transmission electron microscopy characterization was used for determining the structural properties of the Pd nanocatalyst.     

Electrochemical and photocatalytic hydrogen evolution by an electron‐deficient cobalt tris(ethoxycarbonyl)corrole complex

An electron‐deficient flat 5,10,15‐tris(ethoxycarbonyl)corrole (TECC) cobalt complex, [Co(TECC)(Py)₂] ( 1 ; py = pyridine), was prepared and employed as a catalyst for homogeneous hydrogen evolution. It turns out that water can be successfully used as a proton source in acetonitrile–water (2:3 v /v) solvent system for electrocatalytic hydrogen evolution. Complex 1 is also an efficient photocatalyst for hydrogen generation from aqueous solution, an example of the first application of metal corrole as photocatalyst for hydrogen production.     

A Visible‐Light‐Induced α‐H Chlorination of Alkylarenes with Inorganic Chloride under NanoAg@AgCl

An efficient, photocatalytic chlorination of alkylarene α‐H groups using NaCl/HCl as a chlorine source has been developed, which involves a radical mechanism under visible‐light (including sunlight) conditions. A chlorine radical is proposed to be formed by an electron transfer from chloride ion to O₂ in air through the bandgap hole of the semiconductor AgCl. The chlorination protocol is characterized by its use of natural sunlight or other visible light, mild conditions, cheap source of chlorine, green solvent, and high selectivity. The yield of benzylchloride is 95 % with a toluene conversion as high as 40 %, which rivals traditional chlorination methods.     

A short review on recent progress of Bi/semiconductor photocatalysts: The role of Bi metal

Bi/semiconductor photocatalysts have extensively been applied in the production of hydrogen, CO₂ reduction and environmental remediation in recent years. This short review summarizes the role of Bi metal as a plasma photocatalyst and cocatalyst. As a cocatalyst, Bi metal can be electron/hole trappers, charge transfer mediators, or oxygen vacancy coordinators. In addition, the preparation methods of the Bi/semiconductor photocatalysts are also reviewed. Challenges and future research directions related to Bi/semiconductor photocatalysts are discussed and summarized, including the use of advanced characterization techniques to refine the reaction mechanism, the difficulties of preparing Bi single atom catalyst, and the improvement of the reduction ability of Bi-based photocatalysts. This review helps understand the reaction mechanisms of the composite photocatalytic systems containing Bi metal and proposes new perspectives for designing the photocatalysts which can control air pollution via a reductive process.