Bulk photochromism in a tungstate-phosphate glass: a new optical memory material?

In this work, we present a new photochromic tungstate based glass which have both absorption coefficient and refractive index modified under laser exposure. The photosensitive effect is superficial under ultraviolet (UV) irradiation but occurs in the entire volume of the glass under visible irradiation. The effect can be obtained in any specific point inside the volume using an infrared femtosecond laser. In addition, the photosensitive phenomenon can be erased by specific heat treatment. This glass can be useful to substitute actual data storage supports and is a promising material for 3-dimensional (3D) and holographic optical storage.     

含异山梨醇结构单元聚酰亚胺的合成与表征

以异山梨醇为原料,合成了含异山梨醇的二胺单体.将该单体与4,4′-(六氟异丙基)双邻苯二甲酸二酐(6FDA)反应,制备了含异山梨醇结构单元的聚酰亚胺.采用红外光谱、氢核磁共振、紫外光谱和热分析等手段,对产物的结构、热性能及光学性能等进行了表征.结果表明,所得到的聚酰亚胺具有较好的热稳定性和光学性能、并在极性溶剂中具有较好的溶解性.     

Polyimide Dendrimers Containing Multiple Electron Donor–Acceptor Units and Their Unique Photophysical Properties

A high‐yielding synthesis of a series of polyimide dendrimers, including decacyclene‐ and perylene‐containing dendrimer D6 , in which two types of polyimide dyes are present, is reported. In these constructs, the branching unit is represented by trisphenylamine, and the solubilizing chains by N‐9‐heptadecanyl‐substituted perylene diimides. The photophysical properties of the dendrimers have been studied by absorption, steady‐state, and time‐resolved emission spectroscopy and pump–probe transient absorption spectroscopy. Photoinduced charge‐separated (CS) states are formed on the femtosecond timescale upon visible excitation. In particular, in D6 , two different CS states can be formed, involving different subunits that decays independently with different lifetimes (ca. 10–100 ps).     

Enhanced photocatalytic activity of ZnO nanoparticles by surface modification with KF using thermal shock method

ZnO nanoparticles were modified with KF using thermal shock method at various temperatures in order to improve the photocatalytic activity of ZnO under both UVA and visible light irradiation. The influences of KF-modification on the crystal structure, morphology, UV–visible absorption, specific surface area as well as surface structure of ZnO were respectively characterized by XRD, FE-SEM, UV–Visible diffuse reflectance, N₂ adsorption and XPS spectroscopy. The photocatalytic activity was evaluated via the degradation of methylene blue under UVA irradiation. According to the results, the thermal shock process with KF did not modify the structure, the particle size and the optical properties of ZnO nanoparticles but successfully increase their UVA and visible light induced photocatalytic activity. This enhancement of activity may be attributed to the increase of surface hydroxyl groups and zinc vacancies of modified ZnO samples.     

可见光响应的LaVO4/TiO2 纳米管的合成、表征及对气相甲苯的光催化性能

通过水热方法合成了可见光响应的LaVO4/TiO2纳米管, 采用XRD, TEM, 氮气吸附-脱附以及表面光电压谱对样品进行了表征. 以气相甲苯为典型污染物, 研究了制备样品在可见光(λ＞420 nm)条件下的光催化性能. 实验结果表明, LaVO4的复合使TiO2的粒径减小, 比表面积增大, 光响应范围向可见光偏移. 光催化实验结果表明, 在可见光条件下, LaVO4/TiO2纳米管降解甲苯的效率比其它样品高, 与纯TiO2纳米管相比, 降解效率提高了47%.     

Silica aerogel–poly(ethylene‐co‐vinyl acetate) composite for transparent heat retention films

Poly(ethylene‐co‐vinyl acetate) (EVA) plastic films are widely used for solar coverings including photovoltaic modules and commercial greenhouse films, but are poor at controlling heat flow. In this work, silica aerogel (SA) nanogels were examined for preparing transparent heat retention EVA films that block far infrared spectra radiation to maintain heat, without compromising the optical performance of the films. SA nanogels were melt‐mixed using a mini twin‐screw extruder with EVA pellets to form SA/EVA composite, which were pressed into thin films with controlled thickness. The composite films were characterized in terms of optical properties using a variety of analytical methods including FTIR, UV–Vis spectroscopy, electron, confocal, and atomic force microscopy. Both thermicity and thermal conductivity of commercial and experimental SA/EVA films were measured. The results demonstrated that the SA/EVA films gave improved infrared retention compared to commercial thermal plastic films without compromising visible light transmission, showing the potential for this approach in next generation heat retention films. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 927–935     

Physicochemcial characteristic of CdS-anchored porous WS2 hybrid in the photocatalytic degradation of crystal violet under UV and visible light irradiation

In this work, we report the synthesis of CdS-incorporated porous WS₂ by a simple hydrothermal method. The structural, morphological, and optical properties of the samples were examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), high resolution X-ray photoelectron spectroscopy (XPS) and UV–visible spectrometry. The photocatalytic activities were established for degradation of crystal violet (CV) under UV and visible light irradiation. The CdS-incorporated porous WS₂ hybrid demonstrated high photocatalytic activity for degradation of CV pollutant compared to pure CdS nanoparticles and porous WS₂ sheets. This result implies that the CdS-incorporated porous WS₂ promoted more electron-hole pair transformation under UV and visible light irradiation. This significant enhancement of photocatalytic efficiency of CdS-incorporated porous WS₂ photocatalyst under visible light can be ascribed to the presence of CdS nanospheres on the meshed-like WS₂ sheets which potentially improves absorption in the visible range enabled by surface plasmon resonance effect of CdS nanospheres. The photostability and reusability of the CdS-porous WS₂ were examined through recycling experiments.     

Enhanced photoinduced super-hydrophilicity in sol–gel TiO2 thin films with co-doped Sn/Nb

In this work, Sn and Nb co-doped TiO₂ were coated on glazed porcelain substrates via sol–gel dip coating method. Field emission-scanning electron microscopy, transmission electron microscopy, and UV–vis spectrophotometer were used to evaluate thickness and optical properties of the thin films. Surface chemical state of thin films was examined by atomic X-ray photoelectron spectroscopy. Water contact angle on the film surfaces was measured by a contact angle analyzer under solar light irradiation. The optical results indicated that Sn/Nb dopant in TiO₂ thin film changed the absorption edge from ultraviolet to visible light and exhibited excellent photo-catalytic ability for degradation of methylene blue solution under solar irradiation. Wettability results indicated that Sn and Nb dopant ions had significant effect on the hydrophilicity property of thin films.     

多孔超薄g-C3N4纳米片负载Pt复合材料的制备及其光催化性能

以三聚氰胺为前驱体,通过热氧化刻蚀法制备多孔超薄g-C₃N₄纳米片（CNHS）,将其与氯铂酸钾溶液混合后采用原位光化学还原法成功制备了CNHS负载Pt光催化剂（Pt-CNHS）。使用粉末X射线衍射、场发射扫描电子显微镜、X射线光电子能谱、透射电子显微镜、紫外可见漫反射光谱和N₂吸附-脱附测试等技术对所制备样品的结构、形貌、光吸收特性、光电化学性能和比表面积等进行系统分析。并以气相甲苯为目标降解物,研究其光催化性能。结果表明,相对于体相g-C₃N₄（CNB）和CNHS,Pt的引入可以有效增强催化剂对可见光的吸收能力、响应范围及载流子分离效率。与纯g-C₃N₄和CNHS相比,Pt-CNHS在紫外和可见光照射下均表现出更高的光催化降解气相甲苯的活性。此外,也对Pt-CNHS光催化剂在可见光照射下降解气相甲苯的反应历程做了初步研究。     

Preparation and characterization of ZnTiO<Subscript>3</Subscript>–TiO<Subscript>2</Subscript>/pillared montmorillonite composite catalyst for enhanced photocatalytic activity

ZnTiO₃–TiO₂/organic pillared montmorillonite (pMt) composite catalyst was successfully prepared in this paper by immobilizing ZnTiO₃–TiO₂ onto pMt. The composition and texture of the prepared composite catalyst were characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, energy dispersive spectrometry, ultraviolet–visible light (UV–Vis) diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic activity was tested via photocatalytic degradation of methyl blue (MB) under both visible irradiation and UV light. The results indicated that the ZnTiO₃–TiO₂/pMt composite catalyst had an apparent absorption at the area of visible irradiation, and exhibited a higher efficiency of photocatalytic degredation of MB under visible irradiation. This was due to the heterostructure of ZnTiO₃–TiO₂, and the mesoporous structure and specific surface area of the ZnTiO₃–TiO₂/pMt composite. In addition, the results of the radical scavenging experiments showed that the holes and superoxide radicals are responsible for the degradation of MB under visible irradiation.     

Ion-beam irradiation effects on polyimide-UV–vis and infrared spectroscopic study

Ion-beam irradiation effects on polyimide, Kapton™, were studied with respect to optical and electronic properties. Stack films of Kapton™ (12.5 μm thick) were irradiated to various ion beams in air or vacuo at room temperature and subjected to ultraviolet–visible (UV–vis) spectroscopy, and change in absorbance and energy gap is discussed. The UV–vis absorption spectrum, which is assigned to the transition of electrons in benzene rings from π to π* orbital, upon He²⁺ (6 MeV/u) irradiation in air, shifted towards longer wavelength direction for all cases, and the shift was more obvious for higher linear energy transfer (LET) ion beams. The energy gap of the transition was estimated, and the H⁺ and He²⁺ ion beams caused little change in the transition energy gap Eg, while the heavier ions such as C⁶⁺ and Si¹⁴⁺ caused more significant decrease. This decrease is assumed to the structural changes around benzene rings, and the infrared spectroscopy revealed breakage in imide groups next to benzene ring in the repeating unit of polyimide.     

Physical properties and structure of thin conducting ion-beam modified polymer films

In this work, a complex investigation of the film surface composition, chemical bonding, conductivity, optical properties, density, hardness and Young's modulus of ion-beam-modified polyimide films was carried out. It was shown that the partial destruction of chemical bonding under ion bombardment leads to the formation of graphite-like, amorphous carbon islands, which increase the surface film conductivity by several orders of magnitude, from an insulating to a semiconducting region. Strong enhancements of both the conductivity and the optical absorption coefficient occur when the fraction of amorphous carbon clusters dispersed in a polyimide matrix reaches 40 %. The values of hardness, Young's modulus and density at high irradiation doses reach the values typical of a hydrogenated amorphous carbon.     

Three‐Dimensional Macroassembly of Sandwich‐Like,Hierarchical, Porous Carbon/Graphene Nanosheets towards Ultralight,Superhigh Surface Area,Multifunctional Aerogels

A new, ultralight, superhigh surface area, multifunctional aerogel, which is macroassembled from sandwich‐like, hierarchical, porous carbon/graphene nanosheets, is described. The multifunctional aerogel was characterized by means of XRD, SEM, TEM, Raman spectroscopy, and UV/Vis absorption spectroscopy. The multifunctional aerogel had an ultralow density of 8 mg cm^?3 and a superhigh surface area of 2650 m² g^?1. The multifunctional aerogel was thermal stability and compressible. Meanwhile, the multifunctional aerogel exhibited high capacity for the adsorption of oils and organic solvents, unexpectedly high hydrogen adsorption and good electrochemical performance.     

A Z‐Scheme Polyimide/AgBr@Ag Aerogel with Excellent Photocatalytic Performance for the Degradation of Oxytetracycline

A novel Z‐scheme polyimide (PI)/AgBr@Ag aerogel photocatalyst has been successfully synthesized by combining an in situ precipitation method and a supercritical drying method. The as‐prepared PI/AgBr@Ag‐50 (50 wt % AgBr@Ag in PI/AgBr@Ag) aerogel photocatalyst exhibited excellent photocatalytic activity for oxytetracycline degradation with a rate constant of 0.025 min^?1, which was 6.9 and 2.6 times higher than that of the PI aerogel or the AgBr@Ag nanoparticles, respectively. More significantly, the PI/AgBr@Ag‐50 aerogel photocatalyst showed stable cycling, which could be attributed to the high mechanical strength and 3D network of the PI aerogel. The introduction of AgBr@Ag on PI with a heterojunction structure efficiently promoted the separation of electron–hole pairs by a Z‐scheme mechanism. The reduced metallic Ag nanoparticles were found to function as centers for the transfer of electrons from AgBr to PI. This work has revealed a new application for the aerogel PI/AgBr@Ag photocatalyst in environmental protection.     

Sm-doped g-C_3N_4/Ti_3C_2 MXene heterojunction for visible-light photocatalytic degradation of ciprofloxacin

A heterojunction of Sm-doped g-C_3N_4/Ti_3C_2 MXene(SCN/MX) was constructed via prepolymerization and solid mixture-calcination method.The modified g-C_3N_4 presented a hollow porous seaweed-like shape which can increase its specific area and active sites.In SCN/MX composite,the optical properties,no matter optical absorption ability or separation performance of photo-induced electrons and holes,were enhanced.Among them,Sm-doping may play an important role on transferring the photogenerated electrons to suppress their recombination,and Ti_3C_2 MXene would broaden light absorption and further improve the carrier migration efficiency.The SCN/MX presented higher photocatalytic degradation efficiency( 99%) of cipro floxacin under visible light irradiation.The quenching experiments and electron spin-resonance spectroscopy confirmed that the dominated active materials were superoxide radical and holes.The degradation mechanisms of ciprofloxacin(CIP) over the SCN/MX were attacking of the active materials on the piperazine ring and quinolone ring,and the final products were CO_2,H_2O and F~-.     

Fabrication of flame-retardant and smoke-suppressant isocyanate-based polyimide foam modified by silica aerogel thermal insulation and flame protection layers

Because of containing urea groups, flame resistance and smoke releasing behaviors of isocyanate-based polyimide foam (IBPIF) produced using free foaming technology require further improvement. In this work, silica aerogel layers were incorporated into cells of IBPIF through an in situ growth process of silica sol (SS). Compared with silica aerogel particles directly mixed into the foaming slurry, the silica aerogel layers that firmly attached to the pores and surfaces of cells not only provided exceptional thermal insulation and flame protection, but also kept original cellular structure. With increase in ratio of SS mass to IBPIF volume, silica aerogel incorporation dosage was gradually increased. Accompanied by flame resistance was obviously improved and smoke releasing behavior was effectively suppressed. Those were indicated by the improved limiting oxygen index (LOI), decreased heat release rate (HRR), peak of HRR, and specific optical density of smoke (Ds) in trials with pilot flames. Compared with pure IBPIF, when the ratio reached to 5/15 g/cm³, it resulted in LOI increasing from 22.0% to 33.0%, peak of HRR, total smoke production (TSP), and maximum value of Ds decreasing from 174 to 72 kW/m², 1.11 to 0.37 m²/m², 45.90 to 17.45, respectively.     

以工业粉煤灰为原料制备 TiO2/SiO2-Al2O3气凝胶三元复合光催化剂及其催化性能

2-仲丁基-4,6-二硝基苯酚(DNBP)作为杀虫剂、除草剂和烯烃基芳香族化合物阻聚剂而被广泛地应用于工农业生产中.在 DNBP生产和使用过程中,会产生大量难以降解的有机废水,从而对人类和生态环境造成极大危害.因此,开展含 DNBP废水的处理技术和方法研究具有重要的现实意义. TiO2半导体材料由于具有良好的光化学特性和电化学行为,近几十年来一直是光催化领域的研究热点.在能量等于或大于 TiO2的带隙能级的辐照光照射下, TiO2可以产生光生电子/空穴对(e-/h+).光生电子和空穴分别与 TiO2表面被吸附的 H2O和 O2分子反应,生成具有强氧化性的活性羟基自由基(?OH),对硝基酚类有机污染物具有较强的降解能力. TiO2光催化反应属于非均相反应,反应在催化剂的表面进行,催化剂对污染物的吸附是影响其催化降解性能的重要因素.但是,传统 TiO2光催化剂存在比表面积小,对有机污染物吸附能力差,光生电子与空穴易于复合等缺陷,限制了 TiO2光催化技术的进一步发展和在水处理领域中的大规模应用.我们基于气凝胶具有多孔性、大比表面积和高孔隙率的特点,以富含硅、铝的工业废弃物粉煤灰为反应原料,首先利用碱熔法和常压干燥技术制备出 SiO2-Al2O3气凝胶.在此基础上,以钛酸四丁酯(TBOT)为反应前体, SiO2-Al2O3气凝胶为载体,利用酸催化溶胶-凝胶法(sol-gel)制备出 TiO2/SiO2-Al2O3气凝胶三元复合光催化剂.利用 X射线粉末衍射(XRD)、傅里叶变换红外光谱(FT-IR)、透射电子显微镜(TEM)、N2吸附-脱附(BET)、紫外-可见吸收光谱(UV-vis)等分析测试技术对所制备的 TiO2/SiO2-Al2O3气凝胶三元复合光催化剂结构进行了表征.结果显示,在 TiO2/SiO2-Al2O3气凝胶三元复合光催化剂中,粒径尺寸为10~30 nm的锐钛矿型 TiO2纳米颗粒均匀分散在 SiO2-Al2O3气凝胶载体上. TiO2/SiO2-Al2O3气凝胶三元复合光催化剂呈现典型介孔材料的 IV型等温线. SiO2-Al2O3气凝胶的加入极大提高了 TiO2光催化剂的比表面积和对有机污染物的吸附性能,但是对 TiO2光波吸收范围影响不大.在制备出 TiO2/SiO2-Al2O3气凝胶三元复合光催化剂基础上,进一步对其在可见光条件下的光催化性能进行了研究.以500 W的 Xe灯光源模拟自然太阳光, DNBP为探针污染物分子,系统考察了可见光照射条件下溶液 pH值、光催化剂用量、光反应时间、DNBP溶液初始浓度不同因素对 TiO2/SiO2-Al2O3气凝胶三元复合光催化剂催化活性的影响.结果表明, TiO2/SiO2-Al2O3气凝胶三元复合光催化剂对 DNBP有机污染物的吸附率和光降解率明显高于纯 TiO2样品.在 DNBP溶液初始浓度为0.167 mmol/L, pH =4.86,催化剂用量6 g/L,光照时间5 h的条件下, TiO2/SiO2-Al2O3气凝胶三元复合光催化剂对 DNBP的降解率几乎高达100%.根据 Langmuir-Hinshelwood方程,在低浓度下光催化降解反应符合一级反应动力学.所制备的 TiO2/SiO2-Al2O3气凝胶三元复合光催化剂具有良好的稳定性和重复利用性能.重复利用5次后, TiO2/SiO2-Al2O3气凝胶三元复合光催化剂对 DNBP的降解率仍高达90%以上.利用紫外-可见分光光度计、气相-质谱联用仪对 DNBP降解中间产物进行了分析,探讨了 DNBP的光催化降解机理.     

Enhanced photo-catalytic activity of TiO2 nanostructured thin films under solar light by Sn and Nb co-doping

In this study, preparation of Sn and Nb co-doped TiO₂ dip-coated thin films on glazed porcelain substrates via sol–gel process have been investigated. The effects of co-doping content on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD), field emission SEM (FE-SEM), high resolution transmission electron microscopy (HR-TEM), and UV–Vis absorption spectroscopy. Surface chemical state of thin films was examined by atomic X-ray photoelectron spectroscopy (XPS). XRD results suggest that adding impurities has a great effect on the crystallinity and particle size of TiO₂. Titania Rutile phase formation in thin film was promoted by Sn⁴⁺ addition but was inhibited by Nb⁵⁺ doping. The prepared co-doped TiO₂ photo-catalyst films showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of methylene blue (MB) solution under solar irradiation. Comparison with undoped and Sn or Nb-doped TiO₂, codoped TiO₂ shows an obviously higher catalytic activity under solar irradiation.     

A study on the free-radical evolution and its correlation with the optical degradation of 170 keV proton-irradiated polyimide

In this paper, the damage process was investigated on the 170 keV proton-irradiated polyimide, based on the evolution of free radical and its correlation with degradation of the optical transmittance using electron paramagnetic resonance (EPR) and optical-transmittance measurements. The results indicate that the g value of irradiated free radicals keeps at a constant of 2.0025 but the spectral intensity of the free radicals increased with the increasing proton fluence. It is found that during the post-storage after irradiation, the concentration of free radical decreased in an exponential rule with the post-storage time and the free-radical stability can be defined by the corresponding time constant at around 2.3 h. It is interested that the recovery of optical-transmittance follows the same mode as that of free radicals. The mechanisms on the free-radical evolution and the correlation between free radical and optical property are discussed in the paper.     

Multi-step surface functionalization of polyimide based evanescent wave photonic biosensors and application for DNA hybridization by Mach-Zehnder interferometer

The process of surface functionalization involving silanization, biotinylation and streptavidin bonding as platform for biospecific ligand immobilization was optimized for thin film polyimide spin-coated silicon wafers, of which the polyimide film serves as a wave guiding layer in evanescent wave photonic biosensors. This type of optical sensors make great demands on the materials involved as well as on the layer properties, such as the optical quality, the layer thickness and the surface roughness. In this work we realized the binding of a 3-mercaptopropyl trimethoxysilane on an oxygen plasma activated polyimide surface followed by subsequent derivatization of the reactive thiol groups with maleimide-PEG₂-biotin and immobilization of streptavidin. The progress of the functionalization was monitored by using different fluorescence labels for optimization of the chemical derivatization steps. Further, X-ray photoelectron spectroscopy and atomic force microscopy were utilized for the characterization of the modified surface. These established analytical methods allowed to derive information like chemical composition of the surface, surface coverage with immobilized streptavidin, as well as parameters of the surface roughness. The proposed functionalization protocol furnished a surface density of 144 fmol mm⁻² streptavidin with good reproducibility (13.9% RSD, n = 10) and without inflicted damage to the surface. This surface modification was applied to polyimide based Mach-Zehnder interferometer sensors to realize a real-time measurement of streptavidin binding validating the functionality of the MZI biosensor. Subsequently, this streptavidin surface was employed to immobilize biotinylated single-stranded DNA and utilized for monitoring of selective DNA hybridization. These proved the usability of polyimide based evanescent photonic devices for biosensing application.