ZnO纳米柱状阵列表面AgX等离子基元修饰及其可见光光催化活性

采用浸渍法制备了表面AgX（X=I,Br）等离子基元修饰的ZnO纳米柱状阵列,研究了浸渍浓度和时间以及紫外光光照预处理对ZnO纳米柱状阵列可见光光催化活性的影响.采用场发射扫描电子显微镜、X射线衍射仪、紫外可见漫反射吸收光谱以及X射线光电子能谱仪等手段对ZnO纳米柱状阵列的形貌、相组成、禁带宽度及其表面特性进行了表征.结果显示,AgBr颗粒分布于ZnO纳米柱状阵列的顶端及顶端侧面,同时AgBr颗粒之间相互接触而形成网状结构.通过紫外光光照预处理,AgBr表面出现细小颗粒,形成Ag/AgBr/ZnO纳米复合结构.可见光光催化降解甲基橙结果表明,在相同工艺条件下所制AgBr/ZnO的可见光光催化活性明显优于AgI/ZnO,且与浸渍浓度及时间有关.由于ZnO纳米柱状阵列的比表面积大,AgBr的可见光响应特性以及Ag/AgBr纳米结构的表面等离子效应,经过紫外光光照预处理形成的Ag/AgBr/ZnO纳米复合结构表现出最好的可见光光催化活性.     

Solvent-dependent photoresponsive conductivity of azobenzene-appended ionic liquids

A new class of azobenzene-based photoresponsive ionic liquids was prepared and showed reversible modulation of ionic conductivity in specific solvents under alternative UV/visible light irradiation.     

Investigating the effect of ultrasonic irradiation on preparation and properties of conductive nanocomposites

In the present study, the ultrasonic irradiation technique was employed as a new approach to prepare 0-3-dimensional polyaniline/ZnO shell-core composite particles. By taking advantage of the multiple effects of ultrasound, one can break down the aggregates of nanocrystalline ZnO particles. The polymerization of aniline proceeded while the nanoparticles were redispersed by ultrasound, and the synthesized polyaniline deposited on the ZnO particle, which formed polyaniline-coated nanocrystalline composite particles. The material was characterized by using transmission electron microscopy, XRD, scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), and Thermogravimetric analysis (TGA). With increased ZnO content, the H-bonding interaction is strengthened and the characteristic peaks of benzoid and quinoid are shifted. X-ray photoelectron spectroscopy (XPS) shows that the ratio of the number of Zn and N atoms (Zn/N) on the surface is lower than that in the bulk. This is strong evidence for a PANI-encapsulated ZnO nanoparticles structure. The conductivity of the composites obtained through ultrasonic irradiation decreases with increasing ZnO content. Ultrasonic irradiation contributes to the increase in the conductivity compared with conventional stirring. Photocatalytic properties of PANI/ZnO nanocomposites were examined by degrading Reactive Black 5 (RB5) dye under visible light irradiation.     

The effect of light penetration depth on the LCST phase behavior of a thermo‐ and photoresponsive statistical copolymer in an ionic liquid

A reflection cloud point technique allows for rapid screening of light‐dependent phase separation temperatures of thermo‐ and photoresponsive polymer/ionic liquid solutions as a function of sample thickness, molecular weight, and copolymer composition. We systematically investigate the lower critical solution temperature (LCST) phase behavior of poly(benzyl methacrylate‐stat‐(4‐phenylazophenyl methacrylate)). Under UV light, the photoresponsive azobenzene‐based repeat unit becomes more polar as the cis form dominates, increasing its solubility in the ionic liquids 1‐ethyl‐3‐methyl imidazolium and 1‐butyl‐3‐methyl imidazolium bis(trifluoromethanesulfonyl)imide. This light‐dependent polarity change leads to two phase separation temperatures, depending on the illumination wavelength. Under visible light, which drives the azobenzene moiety into the trans ground state, the LCST shows no sample thickness dependence. Under UV light, however, sample thickness plays a significant role. Samples of around 1 mm thickness show no apparent difference under UV and visible light, whereas thinner samples show an increasing difference between the phase separation temperatures with decreasing sample thickness. Neither phase separation temperature exhibits a significant dependence on molecular weight. Increasing the photoresponsive monomer content did not lead to an increase in the difference between the phase separation temperatures at fixed thickness, due to a concomitant increase in UV light absorbed at the sample surface. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 281–287     

Photoliquefiable Ionic Crystals: A Phase Crossover Approach for Photon Energy Storage Materials with Functional Multiplicity

Ionic crystals (ICs) of the azobenzene derivatives show photoinduced IC–ionic liquid (IL) phase transition (photoliquefaction) upon UV‐irradiation, and the resulting cis‐azobenzene ILs are reversibly photocrystallized by illumination with visible light. The photoliquefaction of ICs is accompanied by a significant increase in ionic conductivity at ambient temperature. The photoliquefaction also brings the azobenzene ICs further significance as photon energy storage materials. The cis‐IL shows thermally induced crystallization to the trans‐IC phase. This transition is accompanied by exothermic peaks with a total ΔH of 97.1 kJ mol^?1, which is almost double the conformational energy stored in cis‐azobenzene chromophores. Thus, the integration of photoresponsive ILs and self‐assembly pushes the limit of solar thermal batteries.     

ZnO/TiO2复合涂层电极的制备及其光电性能

以氧化铟锡导电玻璃为基材,采用电泳沉积法制备负载型ZnO/TiO2复合涂层,经450℃后续烧结处理后,采用XRD、SEM、EDX和UV-Vis DRS对ZnO/TiO2复合涂层进行表征;在pH=7.00的磷酸盐缓冲溶液中,分别测试ZnO/TiO2复合涂层电极在紫外灯和100 W白炽灯辐照下的电化学阻抗谱、Tafel极化曲线和循环伏安等电化学性质。结果表明:ZnO以200~300 nm晶粒分散于复合涂层中,质量百分比为0.74%;ZnO/TiO2复合涂层在可见光区有一定的吸收;在可见光辐照下ZnO/TiO2复合涂层电极具有较好的光电活性,并对水的分解具有较强的光电催化活性。     

射频溅射制备的多晶ZnO膜表面氧的吸附和脱附

多晶的六角密排的ｃ轴平行于衬底的ＺｎＯ膜已用射频溅射的方法制备出来，一电场感应的氧吸附在这些膜上被观察到由紫外光照射或与Ａｒ离子反应所产生的氧的脱附可使膜的电导率增加６－７个数量级，并且一个积累层在膜的表面显现出来。     

Photochemical control of molecular assembly formation in a catanionic surfactant system

Photochemical control of vesicle disintegration and reformation in aqueous solution was examined using a mixture of 4-butylazobenzene-4'-(oxyethyl)trimethylammonium bromide (AZTMA) as the photoresponsive cationic surfactant and sodium dodecylbenzenesulfonate (SDBS) as the anionic surfactant. Spontaneous vesicle formation was found in a wide-ranging composition of the trans-AZTMA/SDBS system. AZTMA molecules constituting vesicles underwent reversible trans-cis photoisomerization when irradiated with ultraviolet and visible light. Transmission electron microscopy observations using the freeze-fracture technique (FF-TEM) showed that UV light irradiation caused the vesicles to disintegrate into coarse aggregates and visible light irradiation stimulated the reformation of vesicles (normal control). A detailed investigation of the phase state and the effects of UV and visible light irradiation on the AZTMA/SDBS system with the use of electroconductivity, dynamic/static light scattering, and surface tension measurements and FF-TEM observations revealed that in the AZTMA-rich composition (AZTMA/SDBS 9:1) a micellar solution before light irradiation became a vesicular solution after UV light irradiation and visible light irradiation allowed the return to a micellar solution (reverse control). Thus, we could photochemically control the disintegration (normal control) and reformation (reverse control) of vesicles in the same system.     

Control of the Orientation and Photoinduced Phase Transitions of Macrocyclic Azobenzene

Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups ( 1 ) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal–isotropic phase–crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be ?0.84. Heating enhances the thermal cis‐to‐trans isomerization and subsequent cooling returned crystals of the trans/trans isomer.     

均相沉淀法合成纳米ZnO及其光催化性能研究

以ZnSO_4、尿素为原料,采用均相沉淀法在90 ℃合成出了纳米ZnO,并就反应 温度、反应时间、反应物浓度及物料配比等条件对产物的影响进行了探讨。XRD物 相分析,产物为六方晶系;TEM形貌观察,粒子基本为球形,平均粒径20 nm;并用 IR,TG-DTA等测试手段对其进行了表征。利用紫外-可见分光光度计测试了光吸收 性能,发现纳米氧化锌对200～380 nm波长范围的光有很强吸收性,在可见光范围 内,也有较强的吸收。利用纳米氧化锌作为光催化剂对有机染料溶液进行了降解实 验,发现在日光照射60 min后,对酸性大红4BE的降解率可达100%。     

Preparation, characterization, and photocatalytic activity of polyaniline/ZnO nanocomposite

Polyaniline (PANI)/zinc oxide (ZnO) nanocomposite was synthesized by in-situ polymerization. X-ray diffraction patterns, UV?Cvisible spectroscopy, SEM, and TEM were used to characterize the composition and structure of the nanocomposite. Nanostructured PANI/ZnO composite was used as photocatalyst in the photodegradation of methylene blue dye molecules in aqueous solution. The photocatalytic activity of PANI/ZnO nanocomposite under UV and visible light irradiation was evaluated and was compared with that of ZnO nanoparticles. ZnO/PANI core?Cshell nanocomposite had greater photocatalytic activity than ZnO nanoparticles and pristine PANI under visible light irradiation. According to these results, application of PANI as a shell on the surface of ZnO nanoparticles causes the enhanced photocatalytic activity of the PANI/ZnO nanocomposite. Also UV?Cvisible spectroscopy studies showed that the absorption peak for PANI/ZnO nanocomposite has a red shift toward visible wavelengths compared with the ZnO nanoparticles and pristine PANI. The effect of different operating conditions on the photocatalytic performance of PANI/ZnO nanocomposite in the photodegradation of methylene blue dye molecules was investigated in a bath experimental setup.     

Photochromic characteristics of monodisperse microcapsules containing azobenzene derivative-doped nematic liquid crystals

Highly mono-sized dye-doped liquid crystal (LC) microcapsules were prepared by the solute codiffusion method for application in photoswitchable devices. Azobenzene derivatives, which can be photoisomerized by irradiation with UV (366 nm) and visible (433 nm) light, were used as a photoresponsive dichroic dye. The microcapsules have a spherical shape and a single dye-doped LC domain. After UV light (366 nm) irradiation, PDLC films prepared using the microcapsules attained a photostationary state within 10 min and this state maintained stability. PDLC films made by employing a dichroic dye having electron donor and acceptor groups in the molecule showed especially good photoisomerization properties. The reversible trans-cis -photoisomerization occurred sharply by irradiating alternately with visible and UV light.     

Photogeneration and decay of charge carriers in hybrid bulk heterojunctions of ZnO nanoparticles and conjugated polymers

The photogeneration and decay of charge carriers in blend films of ZnO nanoparticles (diameter 5 nm) and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) or poly(3-hexylthiophene) (P3HT) were studied by means of microwave-photoconductance measurements. Excitation of the polymer in the visible spectrum was found to lead to a transient photoconductance due to dissociation of excitons at the interface between ZnO and the conjugated polymer. From the similar decay kinetics of the photoconductance and the effects of UV illumination, it is concluded that the measured photoconductance is due to electrons in ZnO. Increasing the weight fraction of ZnO in the blend films leads to a higher photoconductance. This is attributed to enhanced formation of mobile electrons by interfacial dissociation of excitons at clusters of ZnO nanoparticles rather than at individual nanoparticles. The dependence of the photoconductance on the weight fraction of ZnO is found to be different for ZnO:MDMO-PPV and ZnO:P3HT blends. This is most likely due to the presence of a smaller number of relatively large ZnO clusters in ZnO:P3HT blends and a shorter exciton diffusion length, as compared with ZnO:MDMO-PPV blends. After exposure of the blend films to UV light, a significant increase in the magnitude and the lifetime of the photoconductance is observed. This is explained in terms of the filling of electron traps in ZnO by UV exposure.     

Synthesis and Optical Properties of Ce-doped ZnO

ZnO nanorods were synthesized using the sol-gel method, and the effects of annealing temperature and Ce doping on the morphologies and optical properties of ZnO nanostructures were investigated in detail. The XRD measurements showed that the as-synthesized ZnO nanostructures had a hexagonal wurtzite structure. SEM images showed that uniform nanorods formed at 900 °C. Photoluminescence measurements showed an ultraviolet emission peak and a relatively broad visible light emission peak for the samples sintered at different temperatures. The UV emission peak bathochromically shifted when the annealing temperature rose from 850 to 1000 °C. Ce doping decreased the synthesized temperature of the ZnO nanorods to 500 °C, and the UV peaks hypsochromically shifted.     

Photochromic characteristics of monodisperse microcapsules containing azobenzene derivative-doped nematic liquid crystals

Highly mono-sized dye-doped liquid crystal (LC) microcapsules were prepared by the solute codiffusion method for application in photoswitchable devices. Azobenzene derivatives, which can be photoisomerized by irradiation with UV (366 nm) and visible (433 nm) light, were used as a photoresponsive dichroic dye. The microcapsules have a spherical shape and a single dye-doped LC domain. After UV light (366 nm) irradiation, PDLC films prepared using the microcapsules attained a photostationary state within 10 min and this state maintained stability. PDLC films made by employing a dichroic dye having electron donor and acceptor groups in the molecule showed especially good photoisomerization properties. The reversible trans-cis -photoisomerization occurred sharply by irradiating alternately with visible and UV light.     

Photoreversible DNA condensation using light-responsive surfactants

A means to control DNA compaction with light illumination has been developed using the interaction of DNA with a photoresponsive cationic surfactant. The surfactant undergoes a reversible photoisomerization upon exposure to visible (trans isomer, more hydrophobic) or UV (cis isomer, more hydrophilic) light. As a result, surfactant binding to DNA and the resulting DNA condensation can be tuned with light. Dynamic light scattering (DLS) measurements were used to follow lambda-DNA compaction from the elongated-coil to the compact globular form as a function of surfactant addition and light illumination. The results reveal that compaction occurs at a surfactant-to-DNA base pair ratio of approximately 7 under visible light, while no compaction is observed up to a ratio of 31 under UV light. Upon compaction, the measured diffusion coefficient increases from a value of 0.6 x 10(-8) cm2/s (elongated coil with an end-to-end distance of 1.27 microm) to a value of 1.7 x 10(-8) cm2/s (compact globule with a hydrodynamic radius of 120 nm). Moreover, the light-scattering results demonstrate that the compaction process is completely photoreversible. Fluorescence microscopy with T4-DNA was used to further confirm the light-scattering results, allowing single-molecule detection of the light-controlled coil-to-globule transition. These structural studies were combined with absorbance and fluorescence spectroscopy of crystal violet in order to elucidate the binding mechanism of the photosurfactant to DNA. The results indicate that both electrostatic and hydrophobic forces are important in the compaction process. Finally, a DNA-photosurfactant-water phase diagram was constructed to examine the effects of both DNA and surfactant concentration on DNA compaction. The results reveal that precipitation, which occurs during the latter stages of condensation, can also be reversibly controlled with light illumination. The combined results clearly show the ability to control the interaction between DNA and the complexing agent and, therefore, DNA condensation with light.     

Photoconductive UV Detectors Based on ZnO Films Prepared by Sol-Gel Method

Highly c-axis oriented ZnO thin films were deposited on single crystal Si (111) substrates by sol-gel method. The photoconductive UV detectors based on ZnO thin films, being a metal-semiconductor-metal (MSM) structure with interdigital (IDT) configuration, were fabricated by using Au as contact metal. The characteristics of dark and photocurrent of the UV detector, the UV photoresponse of the detector were investigated. The linear current-voltage (I-V) characteristics under both forward and reverse bias exhibit ohmic metal-semiconductor contacts. Under illumination using monochromatic light with a wavelength of 365 nm, photo-generated current arrived at 44.89 μ A at a bias of 6 V. The detector exhibits an evident wide-range spectral responsivity and shows a trend similar to that in photoluminescence (PL) spectrum. PL spectrum of detector exhibits two peaks, one is the near band edge emission, and another is the deep-level emission in the visible region.     

Photoresponsive J-aggregation behavior of a novel azobenzene-phthalocyanine dyad and its third-order optical nonlinearity

The photoresponsive J-aggregation behaviors of a novel azobenzene-substituted zinc phthalocyanine (azo-ZnPc dyad) were studied by UV/vis, fluorescence, and (1)H NMR spectroscopy. Upon illumination with 365 nm UV light, the trans-cis isomerization of azobenzene can efficiently reduce the steric hindrance around the peripheral oxygen atom of azo-ZnPc, shortening the possible distance between two phthalocyanine molecules and, consequently, greatly improving the tendency of J-aggregation of azo-ZnPc dyad. The third-order optical nonlinearities of the photoresponsive J-aggregates (before and after illumination) were measured by a Z-scan technique at 532 nm with a pulse duration of 25 ps. The Z-scan spectra revealed that all the samples possessed large positive nonlinear refraction and positive nonlinear absorption, exhibiting a self-focusing effect and reverse saturable absorption, respectively. The second molecular hyperpolarizabilities of the dyad in two conditions were measured to be 3.87 x 10(-30) and 4.82 x 10(-30) esu, respectively. All the results suggest that the azo-ZnPc dyad has potential in the field of nonlinear optics applications.     

Loading Photochromic Molecules into a Luminescent Metal–Organic Framework for Information Anticounterfeiting

Stimuli‐responsive photoluminescent materials have attracted considerable attention owing to their potential applications in security protection because the information recorded directly in materials with static luminescent outputs are usually visible under either ambient or UV light. Herein, we realize reversible information anticounterfeiting by loading a photoswitchable diarylethene derivative into a lanthanide metal–organic framework (MOF). Light triggers the open‐ and closed‐form isomerization of the diarylethene unit, which respectively regulates the inactivation and activation of the photochromic FRET process between the diarylethene acceptor and lanthanide donor, resulting in reversible luminescence on–off switching of the lanthanide emitting center in the MOF host. This photoresponsive host–guest system allows for reversible multiple information pattern visible/invisible transformation by simply alternating the exposure to UV and visible light.     

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.