Thermo-Responsive ZnPc-g-TiO2-g-PNIPAM Photocatalysts Sensitized with Phthalocyanines for Water Purification under Visible Light

A novel thermo-responsive 2,9(10),16(17),23(24)-tetrakis[(3-carboxyacrylamide) phthalocyaninato] zinc (ZnPc)-g-TiO₂-g-poly(N-isopropylacrylamide) (PNIPAM) photocatalyst modified with phthalocyanines was prepared. The photocatalyst exhibited thermo-responsive properties due to the introduction of PNIPAM, which performed recovery for reuse above the lower critical solution temperature (LCST, about 26 °C). ZnPc-g-TiO₂-g-PNIPAM effectively expanded the light response range to the visible light region and inhibited the recombination of electron–hole pairs, which enhanced the performance of the photocatalyst. As expected, ZnPc-g-TiO₂-g-PNIPAM (0.3 g/L) exhibited excellent photocatalytic performance for the removal of Rhodamine B (RhB, 1.0 × 10⁻⁵ mol/L) and methylene blue (MB, 1.0 × 10⁻⁵ mol/L) under visible light, which reached 97.2% and 88.6% at 20 °C within 40 min, respectively. Furthermore, the influence of temperature upon photocatalytic performance was also investigated. When the temperature increased from 20 °C to 45 °C, the removal of RhB decreased by approximately 53.8%. The stability of the photocatalyst demonstrated that the photocatalytic activity was still above 80% for the removal of RhB after 3 cycles. Above all, this work provided an intelligent thermally responsive photocatalyst based on phthalocyanine for water purification under visible light.     

Additive-free controllable fabrication of bismuth vanadates and their photocatalytic activity toward dye degradation

Bismuth vanadates (BiVO₄) with various crystal structures (tetragonal scheelite, monoclinic scheelite, and tetragonal zircon) and morphologies (sphere-, nanosheet-, dendrite-, and flower-like) were controllably fabricated by using a mild additive-free hydrothermal treatment process under the different preparation conditions. The crystal structures, morphologies, and photophysical properties of the products were well-characterized. Subsequently, their UV- as well as visible-light photocatalytic performance was evaluated via dyes rhodamine B (RB) and methylene blue (MB) degradation. Special attention was paid to evaluate the correlation of the reactivity with crystal structure, morphology, and electronic structure of as-prepared BiVO₄ samples.     

Preparation of nano-sized platinum metal catalyst using photo-assisted deposition method on mesoporous silica including single-site photocatalyst

Pt particles in a uniform dispersion were successfully synthesized on single-site photocatalyst (Ti-containing mesoporous silica (Ti-HMS)) under UV-light irradiation by a photo-assisted deposition (PAD) method. Using an aqueous solution of H₂PtCl₆ as a precursor, the nano-sized Pt metal particles were deposited directly on the photo-excited tetrahedrally coordinated titanium oxide moieties within the framework of mesoporous silica (PAD-Pt/Ti-HMS). The Pt catalysts were characterized by means of XRD, Pt L_III-edge XAFS, CO adsorption, and TEM analysis. It was demonstrated that Pt particles had mean diameter of 4 nm in a narrow size distribution. Meanwhile, Pt particles loaded by a conventional impregnation method (imp-Pt/Ti-HMS) showed a wide size distribution ranging from 2 to 30 nm. The PAD-Pt/Ti-HMS catalyst was more active in the CO oxidation than the conventional impregnated imp-Pt/Ti-HMS catalyst. It is suggested that the PAD method using single-site photocatalyst is a useful and unique technique to prepare fine and uniform Pt nanoparticles.     

大规模合成具有氧空位的多孔Bi2O3用于有效降解亚甲基蓝

光催化降解有机污染物由于其具有低能耗和绿色环保的特点,已经成为研究的热点. 氧化铋纳米晶体的带隙在2.0∽2.8 eV之间,利用它催化可见光降解有机污染物具有较高的活性,从而引起了越来越多的关注. 尽管近年来已经开发了几种制备Bi₂O₃基半导体材料的方法,但是仍然难以用简单的方法大规模地制备高活性的Bi₂O₃催化剂. 因此,开发简单可行的大规模制备Bi₂O₃纳米晶体的方法对于工业废水处理的潜在应用具有重要意义. 本文通过蚀刻商用BiSn粉末,然后进行热处理,成功地大规模制备了多孔Bi₂O₃. 获得的多孔Bi₂O₃在亚甲基蓝(MB)的光催化降解中表现出优异的活性和稳定性. 对该机理的进一步研究表明,多孔Bi₂O₃合适的能带结构允许生成活性氧物种,例如O₂^-·和·OH,可有效降解MB.     

Photocatalytic Nanoheterostructures and Chemically Bonded Junctions Made by Solution-Based Approaches

While single compound semiconductors were initially used for photocatalysis, combining two compounds to form a heterojunction significantly increases the photocatalysis performance. This review will outline how heterojunctions are superior, explain the different heterostructure architectures assembled from nanoparticles, and discuss the importance of achieving a large and quality contact in the junction, the heterojunction. Reference is made to methods for increasing the charge carrier performance and reducing recombination. Solution-based synthesis approaches, have been selected as the preferred route of manufacture, for the low cost scalability, and ability to combine a larger number of compounds. The main objective of this review article is to provide insight to the range of chemical solution-based methods for forming chemically bonded junction in nanoheterostructures for photocatalysis. Methods include chemical precipitation, impregnation, chemical bath deposition, hot injection, solvothermal, photo-deposition, electrochemical deposition, cation exchange and linker assisted assembly. The synthesis of different photocatalysts is addressed for each synthesis method. Solution synthesis is offered for coupling oxide semiconductors (i.e. TiO₂, ZnO, WO₃, Fe₂O₃, BiVO₄) with other oxides or metal chalcogenide quantum dots or metallic plasmonic nanoparticles.     

Sonoprecipitation dispersion of ZnO nanoparticles over graphene oxide used in photocatalytic degradation of methylene blue in aqueous solution: Influence of irradiation time and power

In this paper, ZnO/Graphene Oxide (ZnO/GO) is synthesized via ultrasound assisted precipitation method and the effect of power and ultrasound time irradiation is studied on photocatalyst properties. The synthesized samples are used for methylene blue (MB) degradation as an organic water pollutant. Physicochemical properties of the samples are investigated by XRD, FESEM, EDX, BET-BJH, FTIR and DRS techniques. Moreover, pH_pzc of the sample with the best performance is calculated to study the effect of acidity on the photocatalyst efficiency in photocatalytic process. Ultrasound has a positive effect on photocatalyst performance that is because of its effect on distribution of particles and semiconductor band gap, but it has no effect on photostability of the nanocomposite. Sonication has modified distribution of particles by enhancing the active sites for oxidation process. Making structural gaps by ultrasound irradiation increases available surface area which has a similar effect on photocatalyst performance. Graphene oxide as electron collector and transporter prevents electron-hole recombination and it can be an acceptable reason for enhancement at photocatalyst performance. Finally, some of operational parameters such as pH, photocatalyst loading and dye concentration are investigated.     

Zinc oxide nanoparticles reinforced conducting poly(aniline-co-p-phenylenediamine) nanocomposite

Zinc oxide (ZnO) nanoparticles were synthesized by thermal decomposition method and formation of composite with conducting copolymer via in situ chemical oxidative polymerization. Transmission electron microscopy showed that the nanoparticles with an average diameter of 15–25?nm were dispersed in the copolymer matrix. The comonomer molecules were adsorbed on the surface of ZnO particles and then polymerized to form core–shell nanocomposite. The obtained nanocomposite showed a significant improvement in the thermal behavior as indicated by thermogravimetric analysis. The nanocomposite was also confirmed by Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, and X-ray diffraction. Room temperature conductivity of nanocomposite was higher than the value obtained for the pure copolymer. Photocatalytic activity of the nanocomposite was evaluated by measuring the degradation of methylene blue dye under UV irradiation.     

CdS/TiO2/漂珠复合光催化剂制备及其降解高效氯氰菊酯研究

采用溶胶-凝胶-浸渍法制备了Cds/TiO2/漂珠复合光催化剂,通过SEM,XRD对其结构进行了表征.以高效氯氰菊酯(BEC)杀虫剂的光催化降解为模型反应,研究了CdS/TiO2/漂珠的光催化性能,探讨了影响催化剂活性的因素及采用太阳光作光源处理BEC的可行性.结果表明,CdS/TiO2/漂珠投加量为3 000mg·L-1,初始浓度为45 mg·L-1、初始pH为6.5,通气量为200 mL·min-1时间为60 min,BEC降解率分别为92.1%(125W高压汞灯)和79.3%(5 W紫外灯),采用太阳光照射300 min,BEC降解率可达93.4%.BEC的降解反应遵从L-H动力学模型,测得反应速率常数9.80 mg·(L·min)-1,吸附常数4.36×10-3 L·mg-1.     

Immobilization of RuS2 Nanoparticles Prepared in Reverse Micellar System onto Thiol-Modified Polystyrene Particles and their Photocatalytic Properties

RuS₂ nanoparticles, smaller than 3 nm in diameter, were prepared by H₂S gas injection into the AOT/isooctane reverse micellar solution containing RuCl₃ aqueous solution. The nanoparticle size was found to be independent of the W_o (water content) value of the reverse micellar system, as shown by TEM observation. The recovery and immobilization of the RuS₂ nanoparticles from reverse micelles onto thiol-modified polystyrene particles (PSt-SH) were successfully carried out, by the addition of PSt-SH into the reverse micellar solution under conditions of mild stirring. The resulting composites, PSt-RuS₂, showed photocatalytic activity for H₂ generation form aqueous solution containing 2-propanol and Na₂SO₃ as sacrificial electron donors.     

IR and XPS investigation of visible-light photocatalysis—Nitrogen-carbon-doped TiO2 film

To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Nitrogen and carbon doping TiO_2−x−yN_xC_y films were obtained by heating the TiO₂ gel in an ionized N₂ gas and then were calcined at 500 °C. The TiO_2−x−yN_xC_y films have revealed an improvement over the TiO₂ films under visible light (wavelength, 500 nm) in optical absorption and photocatalytic activity such as photodegradation of methyl orange. X-ray photoemission spectroscopy, infrared spectrum and UV-visible (UV-vis) spectroscopy were used to find the difference of two kinds of films. Nitrogen and carbon doped into substitutional sites of TiO₂ has been proven to be indispensable for band-gap narrowing and photocatalytic activity.