UV-light and visible-light photochromism of inorganic–organic multilayer films based on polyoxometalate and poly(acrylamide)

Novel UV-light and visible-light photochromic inorganic–organic multilayers composed of polyoxometalates (phosphomolybdic acid (PMoA)) and poly(acrylamide) (PAM) were prepared by the layer-by-layer (LbL) self-assembly method. The grown process, composition, surface topography, and photochromic properties and mechanism of the multilayer films were investigated by ultraviolet–visible (UV–vis) spectra, Fourier transform infrared spectra (FT-IR), atomic force microscopy (AFM), electron resonance spectra (ESR), and X-ray photoelectron spectra (XPS). Irradiation with UV-light or visible-light, the transparent films changed from colorless to blue and showed reversible photochromism. PMoA/PAM LbL films had higher photochromic efficiency under UV-light irradiation than visible-light irradiation. The bleaching process occurred when the films were in contact with O₂ in the dark or heated in air. The photochromic process of PMoA/PAM LbL film was in accordance with radical mechanism.     

Preparation and photochromism of Keggin-type molybdphosphoric acid/silica mesoporous composite thin films

Using tetraethoxysilane and 3-aminopropyltriethoxysilane as the silica sources, amino-functionalized organic/inorganic hybrid mesoporous silica thin films with 2-dimensional hexagonal structure have been synthesized by evaporation induced self-assembly process in the presence of cetyltrimethyl ammonium bromide templates under acid conditions. The Keggin-type molybdphosphoric acid (PMo) is incorporated into the mesoporous silica thin films with amino-groups by wetness impregnation, and the PMo/silica mesoporous composite thin films are obtained. The results of X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and Fourier transform infrared (FTIR) spectra indicate the PMo molecules maintain Keggin structure and are homogeneously distributed inside mesopores. The composite thin films possess excellent reversible photochromic properties, and change from colorless to blue under ultraviolet irradiation. The photochromic mechanism of the composite thin films is studied by ultraviolet-visible (UV-vis), electron spin resonance (ESR) and X-ray photoelectron spectroscopy (XPS) spectra. It is shown that intervalence charge transfer (IVCT) and ligand-to-metal charge transfer (LMCT) are the main reasons of photochromism. PMo anions interact strongly with amino-groups of the mesoporous suface via hydrogen bond and electrostatic force. After ultraviolet irradiation, the charge transfer occurs by reduction of heteropolyanions accompanying the formation of heteropolyblues with multivalence Mo(VI, V), and the bleaching process of composite thin films is closely related to the presence of oxygen.     

Structure and photochromic properties of molybdenumphosphoric acid/TiO<Subscript>2</Subscript> composite films

TiO₂ sol-gel composite films with dropping molybdenumphosphoric acid (PMoA) have been prepared by sol-gel method. The structure and constitute of composite thin films were studied with Fourier transforms infrared spectroscopy (FT-IR) atomic force microscopy (AFM), and X-ray diffraction (XRD) patterns, respectively. The photochromic behavior and mechanism of composite thin films were investigated with ultraviolet-visible spectra (UV-vis) and electron spin resonance (ESR). FT-IR results showed that the Keggin geometry of PMoA was still preserved inside PMoA/TiO₂ composite thin films, and a charge transfer bridge was built at the interface of PMoA and TiO₂ through the Mo-O-Ti bond. Surface topography of the composite film showed obvious changes before/after adding PMoA, and the surface topography of composite films showed obvious changes before/after irradiating as well. Composite thin film had reversible photochromic properties. Irradiated with UV light, transparent films changed from colorless to blue and they can bleach completely with ambient air in the dark. ESR results showed that TiO₂ were excitated by UV light to produce electrons, which deoxidized PMoA to produce heteropolyblues. The photochromic process of PMoA/TiO₂ system was carried through electron transfer mechanism.     

Preparation and Visible-light Photochromism of Phosphomolybdic Acid/Polyvinylpyrrolidone Hybrid Film

The visible-light photochromic hybrid film was constructed by entrapping phosphomolybdic acid（PMoA） into polyvinylpyrrolidone（PVPd） networks. The microstructure, photochromic properties and mechanism were inves- tigated with transmission electron microscopy（TEM）, atomic force microscopy（AFM）, Fourier transform infrared （FTIR） spectroscopy, ultraviolet-visible（UV-Vis） spectra and X-ray photoelectron spectroscopy（XPS）. The results in- dicate that the Keggin geometry of PMoA and the basic structure of PVPd are not destroyed during the composite process. Irradiated with visible light, the transparent PMoA/PVPd film changes color from colorless to blue and ex- hibits reversible photochromism in the presence of oxygen. According to the XPS analysis, the charge-transfer bridge of N-H-O has been built between PMoA and PVPd matrix via non-covalent bonding, and the appearance of Mo5＋ species indicates that the photo-reduction process is in accordance with the proton transfer mechanism.     

多酸含量对无机/高分子复合薄膜结构及光致变色性能的影响

制备了一系列不同浓度的钨磷酸/聚乙烯醇(PWA/PVA)复合薄膜, 通过红外光谱、原子力显微镜、紫外-可见吸收光谱对复合薄膜的结构和光致变色性能进行了研究. 红外光谱分析结果表明, Keggin结构钨磷酸和聚乙烯醇分子的基本结构在复合薄膜中仍然存在, 钨磷酸分子与高分子底物间存在氢键作用, 形成电荷转移桥. 原子力显微镜(AFM)结果表明复合前后PVA薄膜表面形貌发生了显著变化, 复合膜表面形貌随钨磷酸含量的不同而不同. 在紫外光照射下, 复合薄膜由无色变为蓝色. 复合膜的升色速度和褪色速度均随着钨磷酸含量的增加而加快. 这些结果表明钨磷酸含量对复合膜的微结构存在影响, 从而导致了复合膜具有不同的光致变色性能.     

Preparation and photochromic properties of pyrazolones/polyvinyl alcohol composite films

Novel photochromic composite films have been successfully fabricated by dispersing pyrazolone derivative:1,3-Diphenyl-4-(3-chlorobenzal)-5-hydroxypyrazole 4-phenylsemicarbazone (1a) into hydrosol of polyvinyl alcohol (PVA). The microstructure, photochromic behaviors and thermal bleaching properties were investigated by Raman spectroscopy, X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and ultraviolet-visible absorption spectroscopy (UV-vis). The results showed that 1a was not only blended but also well dispersed in the PVA polymer films with a suitable content of chromophore. Upon UV light irradiation, the composite films gradually changed from colorless to yellow and recovered fully to the initial state upon thermal bleaching. The time constants of photochromic reactions were almost the same as those of 1a observed in their crystalline state, indicating that the photochromic phenomenon is barely disturbed by the polymer matrix.     

12-钼磷酸与聚乙烯醇固容体的光致变色及其稳定性

以ESR,XPS,IR和UV-vis等手段,研究12-钼磷酸与聚乙烯醇黄色固容体的光致变色及其稳定性。由测试结果得知,该固容体的光致变蓝色是因其在紫外光照射下的光化学反应产物多价钼(VI,V,IV)配合物呈蓝色,而另一种产物带部分羰基的聚乙烯醇为无色所致。随着它们的生成,后者产物因具有螺旋状结构能与前者产物发生包合作用,从而提高光致变色的稳定性。     

Photochromism and electrochemistry of a dithienylcyclopentene electroactive polymer

A bifunctional substituted dithienylcyclopentene photochromic switch bearing electropolymerisable methoxystyryl units, which enable immobilization of the photochromic unit on conducting substrates, is reported. The spectroscopic, electrochemical, and photochemical properties of a monomer in solution are compared with those of the polymer formed through oxidative electropolymerization. The electroactive polymer films prepared on gold, platinum, glassy carbon, and indium titanium oxide (ITO) electrodes were characterized by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The thickness of the films formed is found to be limited to several monolayer equivalents. The photochromic properties and stability of the polymer films have been investigated by UV/vis spectroscopy, electrochemistry, and XPS. Although the films are electrochemically and photochemically stable, their mechanical stability with respect to adhesion to the electrode was found to be sensitive to both the solvent and the electrode material employed, with more apolar solvents, glassy carbon, and ITO electrodes providing good adhesion of the polymer film. The polymer film is formed consistently as a thin film and can be switched both optically and electrochemically between the open and closed state of the photochromic dithienylethene moiety.     

Fabrication of photosensitive multilayer films based on polyoxometalate and diazoresin

A novel photosensitive organic-inorganic composite film incorporating polyoxometalate, K7[SiW11O39Co(H3P2O7)] (SiW11CoPP), and diazoresin (DR) has been prepared via layer-by-layer (LBL) self-assembly. Under UV irradiation, followed the decomposition of diazonium in DR, the ionic bonds between the adjacent interfaces of the multilayer film convert to covalent bonds. The LBL multilayers were characterized by UV-vis spectroscopy, X-ray photoelectron spectra (XPS), atomic force microscopy (AFM), FTIR spectrum, cyclic voltammograms (CV), and electron spin resonance (ESR) measurements. UV spectroscopy shows that the deposition process is regular and highly reproducible from layer to layer. XPS spectra confirm the incorporation of DR and SiW(11)CoPP into the films. Atomic force microscopy image indicates that the film surface is uniform and smooth. Solvent etching experiment proves that the film has significant stability towards polar solvent. Electrochemical behavior of the multilayers is investigated.     

Visible-light Photochromism of Phosphomolybdic Acid/ZnO Composite

A novel photochromic hybrid ZnO was synthesized by doping with phosphomolybdic acid(PMoA). It could respond to visible light and fade in color when treated with hydrogen peroxide(H₂O₂). The microstructure and photochromic properties were investigated via X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM), transmission electron microscopy(TEM), ultraviolet-visible spectroscopy(UV-Vis) and X-ray photoelectron spectroscopy(XPS). The XRD patterns show that the prepared ZnO is pure and has a hexagonal wurtzite structure. The FTIR results demonstrate the existence of a strong interaction between PMoA and ZnO. Due to PMoA doping, the rough surface morphology of ZnO became smooth, as verified by the SEM images. The TEM images illustrate that pure ZnO exhibits a polycrystalline structure with irregular morphology. PMoA was wrapped on the surface of ZnO. After visible-light irradiation, the composite changed from slight yellow to blue and returned to the original color in the presence of H₂O₂. The composite had good photosensitivity and photochromic reversibility. The photochromic process was in accord with photoinduced electrons transfer mechanism.     

Keggin结构钨磷酸／聚丙烯酰胺复合物的制备及光性质研究

无机 有机复合材料的合成是目前令人关注的研究领域[1 ] ,以杂多化合物作为多核配合物 ,通过化学键或氢键作用与有机底物结合形成电荷转移物质的研究已得到广泛重视[2～7] .本文以Ｋｅｇｇｉｎ结构钨磷酸和聚丙烯酰胺为原料合成了钨磷酸 /聚丙烯酰胺复合物 ,表征了其结构特征及光致变色性质 .1　实验方法Ｋｅｇｇｉｎ结构Ｈ3[ＰＷ1 2 Ｏ40 ]·6Ｈ2 Ｏ按文献 [8]方法制备 ,含水量用热重分析测定 .将聚合度为1 1 0 0 0± 1 1 0的聚丙烯酰胺 (ＰＡＭ ) 0 5ｇ、钨磷酸 0 0 5ｇ分别溶解在 50ｍＬ和 1 0ｍＬ水中 ,两者混合后于 65℃下搅拌反应 2…     

Photochromic polyoxotungstoeuropate K12[EuP5W30O110]/polyvinylpyrrolidone nanocomposite films

A novel photochromic nanocomposite film containing polyoxotungstoeuropate K₁₂[EuP₅W₃₀O₁₁₀] entrapped in polyvinylpyrrolidone has been prepared through a spin-on coating technique. Thus-obtained amorphous nanocomposite film was characterized by IR spectra, UV-vis absorption spectra, XRD, SEM, TG-DTA, and ESR. Results show that polyoxotungstoeuropate interacts with polyvinylpyrrolidone strongly and disperses homogeneously in the matrix. The composite film exhibits good photochromic properties. When irradiated with UV light, the transparent film changes from colorless to blue. Then, bleaching occurs when the film is in contact with ambient air or O₂ in the dark. The photochromism of the composite film is due to charge transfer by reduction of polyoxotungstoeuropate and oxidation of polyvinylpyrrolidone.     

光响应性偶氮聚电解质自组装研究

将3种侧链带有不同偶氮生色团的聚电解质,用逐层浸渍的方法使其组装成多层膜.利用原子力显微镜(AFM)研究了自组装膜的表面形貌以及随着组装层数增加的变化.详细研究了在紫外光的照射下,薄膜内偶氮生色团由反式到顺式构型的光响应转变,以及在暗室中由顺式回复到反式构型的回复特性.与自组装膜的光响应性和相应的旋涂膜进行比较发现,其中的PNAPE/PDAC自组装膜没有明显的光色效应,而PEAPE/PDAC,PPAPE/PDAC具有明显的光色效应.在暗室中,随生色团的结构不同和在不同的凝集态中,由顺式回复到反式构型的速率明显不同.     

Keggin结构钨磷酸/聚乙烯吡咯烷酮复合膜的制备和光致变色性质研究

近年来,由于无机－有机复合材料具有潜在的应用前景和特殊性能,尤其是光致变色性能,引起研究者们的广泛兴趣^[1-3],以杂多化合物为多核配合物,通过化合键或氢键作用与高分子底物结合,形成电荷转移物质,可以大大提高复合材料的化学和物理性能。目前,这一领域的研究在国外已经成为热点^[4-7]。本文以Keggin结构钨磷酸和聚乙烯吡咯烷酮为原料,报道了该类复合物的合成、表征及光致变色性质。     

Thermal conversion of poly(paraphenylene–vinylene) precursor films: XPS and ESR studies

The conversion of the precursor into poly(phenylene–vinylene) (PPV) was studied by means of photoelectron spectroscopy (XPS) and electron spin resonance (ESR) on precursor films synthesized from the polymerization of pxylene-tetrahydrophenium halides. The sulfonium precursor containing chlorine or bromine was thermally converted to PPV and analyzed in situ using the spectrometers. It was found by XPS analysis that both halide precursors were thermally converted into polymer in a range of 190–250°C but traces of bromine were still present at >300 °C in the precursor containing Br. Furthermore, a small amount of oxygen in a ketone structure was also present in fully converted films. The ESR results corroborated the XPS experiments, showing a progressive disappearance of the radical distribution related to sulfur sites in a comparable temperature range. A discussion of the conversion process is given in terms of the modification of the core level spectra from XPS and the g distributions from ESR experiments. © 1997 John Wiley & Sons, Ltd.     

镶嵌钨硅酸的新型有机-无机纳米复合薄膜的制备及光致变色性能研究

将超分子自组装技术与Sol-gel过程相结合,制备了镶嵌Keggin结构钨硅酸的MAAM/VTEOS/TEOS纳米复合薄膜,并采用IR,XRD和TG-DSC等方法对薄膜进行了结构表征.在复合薄膜光照变蓝后,通过UV-Vis和ESR光谱对薄膜的光致变色性能及其机理进行了研究.结果表明,钨硅酸在复合网络中仍保持Keggin结构,与有机-无机复合基体中的-NH₂通过氢键发生强烈的相互作用,经紫外光照后发生电荷转移,[SiW₁₂O₄0]₄^-被还原为[SiW₁₂O₄0]₅^-,同时产生氨基自由基.褪色过程则与氧气存在与否有关,实验结果表明,该薄膜具有良好的光致变色性能,对光有较快的响应恢复速度和良好的可逆重复性.     

Surface characterization and radical decay studies of oxygen plasma‐treated PMMA films

Polymethylmethacrylate (PMMA) films were modified by RF oxygen plasma with various powers applied for different periods, and the effects of these parameters on the surface properties such as hydrophilicity, surface free energy (SFE), chemistry, and topography were investigated by water contact angle, goniometer, X‐ray photoelectron spectroscopy (XPS), and atomic force microscopy, and the types of the created free radicals and their decay were detected by electron spin resonance spectroscopy (ESR). SFE and contact angle results varied depending on the plasma parameters. Oxygen plasma treatment (100 W–30 min) enhanced the hydrophilicity of PMMA surface as shown by decreasing the water contact angle from 70° to 26°. XPS analysis showed the change in the amounts of the present functionalities as well as formation of new groups as free carbonyl and carbonate groups. The roughness of the surface increased considerably from ~2 nm to ~75 nm after 100 W–30 min oxygen plasma treatment. ESR analysis indicated the introduction of peroxy radicals by oxygen plasma treatment, and the intensity of the radicals increased with increasing the applied power. Significant decrease in radical concentration was observed especially for the samples treated with higher powers when the samples were kept under the atmospheric conditions. As a conclusion, RF plasma, causes changes in the chemical and physical properties of the materials depending on the applied parameters, and can be used for the creation of specific groups or radicals to link or immobilize active molecules onto the surface of a material. Copyright © 2012 John Wiley & Sons, Ltd.     

Layer-by-layer quantum dot constructs using self-assembly methods

We describe the creation of CdSe/ZnS quantum dot assemblies using layer-by-layer construction strategies, using self-assembly. In the first approach, a dithiol linker was used to make multilayers of CdSe/ZnS quantum dots, while in the second biotin- and streptavidin-conjugated CdSe/ZnS quantum dots were used to make multilayer constructs. Both the chemical bonding nature and fluorescence spectroscopic properties of quantum dot films were characterized using X-ray photoelectron spectroscopy (XPS) and fluorescence spectroscopy.     

Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes

We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.     

Structure and photochromic properties of molybdenumphosphoric acid/TiO_2 composite films

TiO_2 sol-gel composite films with dropping molybdenumphosphoric acid(PMoA) have been prepared by sol-gel method.The structure and constitute of composite thin films were studied with Fourier transforms infrared spectroscopy(FT-IR),atomic force microscopy(AFM),and X-ray diffraction(XRD) patterns,respectively.The photochromic behavior and mechanism of composite thin films were inves-tigated with ultraviolet-visible spectra(UV-vis) and electron spin resonance(ESR).FT-IR results showed that the Keggin geometry...