PW11O39Co（Ⅱ）（H2O）5-的均相及异相体系可见光催化性能研究

以模型污染物罗丹明B（RhB）的光降解为探针,评估了Keggin型钴取代杂多阴离子PW₁₁O₃₉Co（Ⅱ）（H₂O）^5-（PW₁₁Co）及其异相体系PW₁₁Co/D301R的可见光催化活性,提出了光催化反应的机理,同时考察了催化剂用量、溶液酸度以及溶液中PW₁₁Co和RhB的相互作用对RhB可见光催化降解速率的影响。实验结果表明,PW₁₁Co均相体系及其异相体系PW₁₁Co/D301R对RhB的可见光降解均有较高的光催化活性,但与PW₁₁Co相比,PW₁₁Co/D301R的光催化活性更高。导致RhB降解的主要是羟基自由基。与PW₁₁Co均相体系相比,在PW₁₁Co/D₃₀₁R异相体系中由于PW₁₁Co与RhB的配位作用大为减弱,同时D301R对RhB具有富集作用,因而大大提高了RhB的光催化降解速率。     

ZnFe2O4/Ag/TiO2复合材料的制备及其光催化性能

以硝酸银、钛酸四丁酯、无水氯化锌、六水氯化铁为原料,采用溶胶-凝胶法与溶剂热相结合的方法制备了ZnFe₂O₄/Ag/TiO₂复合材料,通过扫描电子显微镜、能谱分析仪、X射线粉末衍射仪、X射线光电子能谱仪、振动样品磁强计、紫外可见分光光度计对样品进行表征及测试。结果表明： ZnFe₂O₄/Ag/TiO₂-10具有最佳的光催化效果,在紫外和可见光下对染料的降解率都能达到90%以上,具有优异的紫外可见光光催化活性。ZnFe₂O₄/Ag/TiO₂具有独特的磁性,能在外部磁场作用下进行回收利用,这使其在实际应用中成为可能。通过磁分离技术重复回收利用5次后仍然保持优良的光催化性能,说明ZnFe₂O₄/Ag/TiO₂-10具有优异的磁性及较高的光催化循环稳定性。     

骨架结构多孔TiO2薄膜增强染料敏化太阳能电池性能

以空心球状TiO₂为基体、以片状TiO₂为骨架,采用刮刀法制备了染料敏化太阳能电池的多孔TiO₂光阳极薄膜。光电转化效率测试结果表明,当作为骨架支撑材料的片状TiO₂含量为20wt%时,光阳极薄膜组装成太阳能电池的光电转化效率达到最高值4.53%,比商业P25制备的无孔无骨架TiO₂薄膜电池(4.06%)及无骨架结构的多孔TiO₂薄膜电池(4.17%)的性能均有显著提高。当片状TiO₂的最佳含量为20wt%电池薄膜厚度为33 μm时,太阳能电池光电转化效率进一步提升为7.06%。光电性能增强的原因是骨架结构有利于快速传输电子并增大染料吸附量。本研究通过设计制备具有骨架结构的多孔TiO₂薄膜为提高染料敏化太阳能电池性能提供了新的思路。     

Synthesis,Characterization and Properties of a Novel Environmentally Friendly Mono Azo Disperse Dye and Its Application on Polyethylene Terephthalate (PET)

The aim of this research is to achieve the synthesis of a novel mono azo disperse dye containing both a β‐naphthyl acetate group and carboxylic acid ester group and application on PET fabric. In this study the dyeing properties have also been investigated. The synthesized dye was characterized using UV‐Vis, FTIR, ¹H NMR and ¹³C NMR spectroscopic techniques. To investigate alkali‐clearability, both alkali‐hydrolysis behavior and the effect of its fastness properties with regard to PET fabric were examined. This dye showed a reasonable level of hydrolysis under relatively mild alkaline conditions. The application of the dye to PET fabric showed good leveling and building up properties. Estimating fastness properties of the dyed fabric showed excellent wash, rubbing fastness, good light and sublimation fastness. The results furthermore displayed that the synthesized dye offers the option of alkali‐clearing process over that of a conventional reduction‐clearing process. Therefore, the value of Chemical Oxygen Demand (COD), Biological Oxygen Demand (BOD) and water pollution as well as the expenditure of production were decreased.     

The electronic structures and charge transfer properties of tetra(naphthalene‐dione)porphyrins and tetra(naphthalene‐dithione)porphyrins as dye‐sensitized solar cell skeleton

The p‐π conjugation of tetra(naphthalene‐dione)porphyrins and tetra(naphthalene‐dithione)porphyrins is clarified on the basis of density functional theory studies. When carbonyl/thionyl is introduced, π bonds on the molecular skeleton become strong–weak alternated, and the conjugation transforms from “benzene‐type” to “butadiene‐type.” The unidirectional photon‐induced current associated with the p‐π conjugation enables the light‐harvesting efficiency of this kind of molecular skeleton reaches 90% in the range of 300–800 nm. Therefore, these compounds are ideal alternative for panchromatic dye‐sensitized solar cells. © 2013 Wiley Periodicals, Inc.     

Facile Synthesis of 5‐Benzylidene Rhodamine Derivatives under Microwave Irradiation

A series of 5‐benzylidenerhodamine derivatives were synthesized by the cross‐aldol condensation of an aromatic aldehyde with rhodamine or rhodamine acetic acid in sodium acetate/acetic acid under microwave irradiation. The reaction was completed in 8–20 min with 63–94% yields and was environmentally benign with easy workup.     

Micellar Enhanced Ultrafiltration of Reactive Black 5 from Aqueous Solution by Cationic Surfactants

Reactive black 5 (RB-5) dye was removed from a water stream using two cationic surfactants, cetyltrimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC), via micellar enhanced ultrafiltration. Three membranes with different pore size were used for the determination of rejection coefficient and permeate flux of the solution at 1.5 bar trans-membrane pressure (TMP). The two surfactants (CPC and CTAB) played an almost negligible role in rejection efficiency with 5000 and 10,000 molecular weight cut-off membrane (MWCO), respectively. In this case, high rejection and low permeate flux was the result of a larger molecular size of RB-5 DYE being retained by comparatively smaller sized pores of membrane via ultrafiltration. However, CPC and CTAB surfactants showed 83% and 98% rejection coefficient, respectively, at a concentration greater than their CMC values against 30,000 MWCO. Permeate flux remained low and constant in presence of 5000 and 10,000 MWCO with a small variation against 30,000 MWCO for the two surfactants, thereby no appreciable effect on both surfactant concentrations on concentration polarization was estimated. Thus, RB-5 dye alone was determined to be responsible for membrane plugging or concentration polarization and ultimately for low permeate flux. The effect of trans-membrane pressure was also investigated during this study.     

Fast polarisation-insensitive optical shutter supported by backflow in dichroic dye-doped dual-frequency liquid crystal

This paper describes a novel implementation of a dual-frequency liquid crystal optical shutter of the guest–host type. The transmissive state of the filter is obtained by applying a low-frequency electric field that brings the dichroic dye in a homeotropic orientation. The light-absorbing state is realised by a twisted planar configuration for which the absorption is quasi-independent of the polarisation. Switching between the two states occurs in about 1 ms and the devices show no scattering for wavelengths inside or outside the absorption band of the dichroic dye. Simulations and experiments reveal how a twisted state is obtained through the backflow phenomenon.     

Effects on molecular orientation and phase transition of addition of carbon nanotubes into liquid crystalline matrix

For practical guest–host applications, it is important to choose dyes with a high ability of orientation in the liquid crystal (LC) matrix. In this experimental work, two different azo-structured dyes (disperse yellow 3 and 7) were separately doped to each of two different nematic LCs (E7 and ZLI-1132). Their solubilities, textures, phase transition temperatures and order parameters were determined. At the second stage, single-walled carbon nanotubes (SWCNTs) in a small amount were separately added to each of these solutions, and the experiments were repeated as similar to the previous ones. The solubilities of dyes in the LC E7 were lower than those of ZLI-1132. Moreover, the highest order parameter value was attained with yellow 7 dye in ZLI-1132 nematic host. Co-use of nanoparticles (CNTs) as dopant resulted in notable increases in order parameters. These dyes and CNTs did not significantly destabilise the mesomorphic phase of nematic hosts. An appreciable change in textures was not monitored with addition of dopant(s). In addition, it was observed that the narrowing on the temperature range of the LC did not take place with the addition of dopants to the crystal; on the contrary, an increase was recorded.     

Elementary Photoelectronic Processes at a Porphyrin Dye/Single‐Walled TiO2 Nanotube Hetero‐interface in Dye‐Sensitized Solar Cells: A First‐Principles Study

A unique one‐dimensional (1D) sandwich single‐walled TiO₂ nanotube (STNT) is proposed as a photoanode nanomaterial with perfect morphology and large specific surface area. We have thoroughly examined the elementary photoelectronic processes occurring at the porphyrin dye/STNT hetero‐interface in dye‐sensitized solar cells (DSSCs) by theoretical simulation. It is desirable to investigate the interfacial photoelectronic processes to elucidate the electron transfer and transport mechanism in 1D STNT‐based DSSCs. We have found that the photoexcitation and interfacial charge separation mechanism can be described as follows. A ground‐state electron of the dye molecule (localized around the electron donor) is first promoted to the excited state (distributed electron donor), and then undergoes ultrafast injection into the conduction band of the STNT, leaving a hole around the oxidized dye. Significantly, the injected electron in the conduction band is transported along the STNT by means of Ti 3d orbitals, offering a unidirectional electron pathway toward the electrode for massive collection without the observation of trap states. Our study not only provides theoretical guidelines for the modification of TiO₂ nanotubes as a photoanode material, but also opens a new perspective for the development of a novel class of TiO₂ nanotubes with high power‐generation efficiency.