二氧化钛反蛋白石薄膜的制备及其在化学传感器中的应用

用提拉成膜法将单分散295 nm聚甲基丙烯酸甲酯(PMMA)胶体微球自组装成蛋白石光子晶体膜. 在PMMA蛋白石光子晶体膜的空隙里填充15 nm二氧化钛纳米颗粒, 经500 ℃的处理除去PMMA膜板, 制备出大面积, 结构均一的二氧化钛反蛋白石光子晶体膜. 扫描电子显微镜(SEM)观察和X射线光电能谱(XPS)分析表明, 这种二氧化钛反蛋白石光子晶体薄膜是六方紧密堆积. 用这种二氧化钛反蛋白石光子晶体膜对溶液折射率的检测实验表明该传感膜分辨率可达0.01.     

三联噻吩衍生物功能化SiO2反蛋白石光子晶体荧光薄膜的制备及应用

将单分散聚苯乙烯微球乳液与SiO₂溶胶均匀混合后, 于恒温恒湿条件下, 竖直沉积共组装制备得到蛋白石型光子晶体薄膜, 然后利用牺牲模板法制得SiO₂反蛋白石光子晶体薄膜. 该薄膜依次经过浓硫酸与过氧化氢混合液、 3-氨丙基三甲氧基硅烷的甲苯溶液、 三联噻吩的三氯甲烷溶液和硼氢化钠的甲醇溶液处理后, 得到三联噻吩衍生物功能化的SiO₂反蛋白石光子晶体. 结果表明, 制备得到的光子晶体薄膜在512 nm处有荧光发射, 经紫外辐射后荧光猝灭, 甲醛气氛下458 nm处又出现新的荧光发射峰. 在甲醛气氛下20 s即可观察到荧光发射, 空气氛围下可恢复, 10次循环仍可保持强的荧光发射, 可重复性良好. 以无反蛋白石光子晶体结构的三联噻吩衍生物的平滑膜与甲醛作用的体系作为参比, 以330和400 nm聚苯乙烯微球为模板制备的三联噻吩功能化反蛋白石光子晶体, 在甲醛气氛中发射的荧光分别增强47.5和78.6倍. 这是由于光子晶体光子禁带的红带边和蓝带边与荧光发射波长相重叠, 产生了慢光子效应, 极大地增强了发射的荧光强度.     

蛋白石及反蛋白石結構光子晶體

光子晶体是由不同介电常数的材料构成的一种空间周期性结构，它能够在特定方向上禁阻、控制和操纵光子的运动。目前，已制备的光子晶体具有几种不同的结构类型，本文主要综述了蛋白石、反蛋白石结构光子晶体的制备方法及其光子带隙的影响因素。     

甲基丙烯酸/丙烯酰胺双单体共聚反蛋白石光子晶体的制备

以烧结后的二氧化硅光子晶体为模板,采用溶胶凝胶法向模板间隙填充以甲基丙烯酸(MAA)和丙烯酰胺(AM)为双功能单体,N,N’-亚甲基双丙烯酰胺(BIS)为交联剂的聚合物前驱液,制备了甲基丙烯酸/丙烯酰胺共聚(PMAM)双单体反蛋白石凝胶光子晶体.通过紫外可见光谱分析表明,反蛋白石结构的凝胶膜对pH响应范围在4.0～7.0之间.由于其不受离子强度的影响,除了可以作为pH传感器外,还可以作为金属离子及生物小分子等分子印迹光子晶体传感器的基体膜.     

反蛋白石光子晶体凝胶的pH响应

首先采用Stber方法制备了一系列亚微米级单分散二氧化硅小球,而后通过垂直沉降自组装方法制备了颜色鲜艳的二氧化硅三维有序结构胶体晶体模板,最后再采用模板聚合法在220 nm二氧化硅小球自组装的阵列间隙中共聚甲基丙烯酸和乙二醇二甲基丙烯酸酯,经氢氟酸刻蚀二氧化硅模板后得到多孔有序的反蛋白石光子晶体.当pH值从5升至8时,反蛋白石凝胶光子晶体的反射峰波长从514 nm移动至590 nm,颜色变化显著,从蓝绿色变成红色,突变点为pH=6.5,而且pH响应在100 s左右即可达到平衡.对交联剂用量的研究结果表明,随着交联剂乙二醇二甲基丙烯酸酯用量从4%增加到16%,光子晶体响应pH时的红移量减小.     

HCl/NH_3敏感的卟啉-二氧化硅反蛋白石光子晶体荧光传感器

将反蛋白石结构的光子晶体引入到腐蚀性气体检测体系,制备得到卟啉-二氧化硅反蛋白石光子晶体(TPP-SiO_2IOPCs)荧光传感器。相对于空白样,TPP-SiO_2IOPCs传感器实现了氯化氢(HCl)气体检测信号200倍的增强,这主要归因于反蛋白石型光子晶体的大孔结构和慢光子效应。同时,TPP-SiO_2IOPCs传感器对于HCl气体的猝灭效率可达75%,比空白样的提高了25%,而且经HCl气体处理后的传感器通入氨气(NH_3)后,初始的荧光强度几乎完全恢复。在HCl和NH_3条件下进行5个循环后,TPP-SiO_2IOPCs传感器表现出良好的可重复使用性。该研究对于发展高效的荧光传感器提供了新的思路。     

反蛋白石结构光催化剂的制备与应用进展

光子晶体是一种具有光子禁带的周期性结构,在一定的波长范围内,光在晶体的某些方向上是不允许传播的;反蛋白石结构作为一种典型的光子晶体结构,具有慢光效应、多次散射效应和放大光子吸收、发射等特性,可以提高催化剂的传质效率、活性中心的曝光率和其集光性能,因此其在光催化领域受到越来越多的关注.我们综述了反蛋白石结构的光学性质;将...     

硫化镉反蛋白石光子晶体制备及光解水制氢

对硫化镉反蛋白石结构光子晶体薄膜进行了可控合成,用巯基乙酸修饰的纳米晶和P(St-MMA-SPMAP)高分子小球共组装,成功地构筑了反蛋白石结构并用于可见光光解水产氢。结果表明,在可见光(λ≥420 nm)照射下,Cd S-310反蛋白石结构薄膜的光解水产氢性能比硫化镉纳米颗粒提高了一倍。这主要是因为等级孔结构反蛋白石光子晶体特性对催化剂的光催化性能的提升:首先,反蛋白石的周期性结构增加了光子在材料中的传播,提高了催化剂对太阳光的利用率;同时,大孔孔壁是由纳米颗粒堆积而成的,在反应中提供了更多的反应活性位点;此外,孔结构有利于物质的传输和分子的吸附。     

聚苯乙烯光子晶体高效制备

以苯乙烯单体为原料,采用一步聚合自组装法制备了具有蛋白石结构的聚苯乙烯(PS)光子晶体(1);以1为模板制备了反蛋白石结构的TiO2光子晶体(2)来验证1的有序性;探讨了1的制备机理。1和2的结构和形貌经IR,SEM和TEM表征。讨论了乳化剂SDS的用量对PS微球排列有序性的影响。结果表明,SDS用量在30 mg～74 mg时,PS微球的粒径不断减小,微球排列的有序性受到影响;当SDS用量为52 mg时,PS微球排列的有序性最佳,能够形成蛋白石结构的1;2在大范围内有序排列进一步证明了1的高度有序性。     

胶体自组装法形成光子带隙材料

光子带隙晶体使人们可以有效地控制和操纵光子,但是构建光子晶体,尤其是近红外及可见光区域的光子晶体是一个困难的工作,它对材料提出了很高的要求.本文从化学的角度,利用自组装方法,对胶体晶体和反蛋白石等类光子带隙材料包括半导体、金属、金属氧化物、聚合物、染料等进行较全面的介绍,同时介绍了如何从这些材料获得光子带隙.     

Photo-induced Birefringence of Azo-dye Based on Three-dimensional Opal Photonic Crystals

A series of three-dimensional opal photonic crystals based on the polymer was synthesized and applied in the field of photo-induced birefringence. The data show that the photo-induced birefringence(PIB) of pure Sudan III film could be enhanced by increasing the thickness of azo films. When Sudan III was distributed on the three-dimensional opal photonic crystals, the photo-induced birefringence process could be modulated. In addition, the data also exhibit that the PIB processes with different pumping polarization directions are sensitive to the role of photonic crystals. The results could be beneficial to further understanding the photo-induced birefringence and utilizing the photonic crystals.     

胶体晶体自组装排列进展

自组装排列胶体晶体是发展光子晶体等亚微米周期有序结构及新型光电子器件十分重要的环节.高电荷密度单分散胶体球在较弱的离子强度和稀浓度下会自发排列形成紧密堆积的周期性结构(ccp),常常是面心立方(fcc),科学家们以此为基础发展了多种结晶化胶体粒子的方法,包括重力场沉积、电泳沉积、胶体外延技术、垂直沉积、流通池、物理束缚排列及其他的许多方法.目前排列的胶体粒子基本为球形,材料也多为SiO2、PS、PMMA,此外一些复合粒子,主要为核壳粒子的排列这里也稍作介绍,这些方法及其变通的使用可以形成类蛋白石及反蛋白石结构,最终实现光子带隙及其它多种用途。     

Fabrication of Cs2.5H0.5PW12O40 three-dimensional ordered film by colloidal crystal template

A three-dimensional ordered polyoxometalate periodic film was synthesized using dodecatungstophosphoric acid (H₃PW₁₂O₄₀) and Cs₂CO₃ as precursors and colloidal crystals as templates by an inverse opal method. The samples were characterized by elemental analysis, XRD, IR spectra, UV-Vis diffuse reflectance spectra (DR-UV-Vis) and SEM techniques. This arrayed film constructed by pure cesium salt of dodecatungstophosphoric acid Cs_2.5H_0.5PW₁₂O₄₀ nanoparticles shows well-defined lamellar array with inverse opal structure, which exhibits a well-defined photonic band gap.     

Inverse opal photonic crystal of chalcogenide glass by solution processing

Chalcogenide opal and inverse opal photonic crystals were successfully fabricated by low-cost and low-temperature solution-based process, which is well developed in polymer films processing. Highly ordered silica colloidal crystal films were successfully infilled with nano-colloidal solution of the high refractive index As(30)S(70) chalcogenide glass by using spin-coating method. The silica/As-S opal film was etched in HF acid to dissolve the silica opal template and fabricate the inverse opal As-S photonic crystal. Both, the infilled silica/As-S opal film (Δn ~ 0.84 near λ=770 nm) and the inverse opal As-S photonic structure (Δn ~ 1.26 near λ=660 nm) had significantly enhanced reflectivity values and wider photonic bandgaps in comparison with the silica opal film template (Δn ~ 0.434 near λ=600 nm). The key aspects of opal film preparation by spin-coating of nano-colloidal chalcogenide glass solution are discussed. The solution fabricated "inorganic polymer" opal and the inverse opal structures exceed photonic properties of silica or any organic polymer opal film. The fabricated photonic structures are proposed for designing novel flexible colloidal crystal laser devices, photonic waveguides and chemical sensors.     

真空填充胶晶模板法快速制备三维有序大孔二氧化钛

以丙烯酸修饰的聚苯乙烯（PS）胶体晶体为模板,采用“三明治-真空”填充法将钛酸四丁酯的乙醇溶液填充到模板间隙中,煅烧除去模板快速高效制备了表面无覆盖层的三维有序大孔二氧化钛（3DOM TiO2）材料。 制备的3DOM TiO2具有典型的反蛋白石结构,孔壁完整且孔径大小均匀,呈六方密堆积的FCC结构。 其孔径为230 nm左右,收缩率仅为14%,孔与孔之间由小窗口相连。 XRD分析表明,500 ℃下煅烧制备的3DOM TiO2为锐钛矿晶型。     

PAM-PAA microgel inverse opal photonic crystal and pH response

The colloidal crystal template or opal with a closed-packed face-centered cubic (fcc) lattice was prepared from monodisperse polystyrene (PS) spheres by vertical sedimentation.The template provided void space for infiltration of monomer precursor composed of acrylate acid,acrylamide and ammonium persulfate,as well as microgel from the subsequent copolymerization.The sample was immersed in dimethylbenzene for completely removing PS spheres to form PAM inverse opal hydrogels (IOH_(PAM)) or PAM/PAA inverse opal hydrogels (IOH_(PAM/PAA)) photonic crystals.The PS spheres were replaced by air spheres,which interconnected each other through the windows.The study of responses to pH show that there are two peaks for both IOH_(PAM) and IOH_(PAM/PAA) films,but the IOH(PAM/PAA) peaks shift to higher pH,and the peaks are independent with the AA content. (?)2007 Xiao Dong Wang.Published by Elsevier B.V.on behalf of Chinese Chemical Society.All rights reserved.     

Polymorphic transitions mediated by surfactants in liquid crystal nanodroplet

Recently, various techniques have been developed using photonic crystals. Liquid crystals (LC) confined in a nanodroplet mimicked photonic crystals, such as those of opal. Therefore, investigating the phase behaviour of LC molecules in nanodroplets is very important in the next-generation optical field. In this study, the chemical interaction between surfactants and LCs in nanodroplets is reproduced using a dissipative particle dynamics method. We identify the phase behaviour of LCs and investigate how the chemical interaction affect on the orientation of LCs. In particular, by adding surfactant molecules, various morphological behaviours were observed in the LC nanodroplet. The phase transition temperature varied depending on R_ND (amount of surfactant molecules). Furthermore, difference of the self-assembly structure also appeared inside the droplet depending on R_ND. Our simulation offers a theoretical guide to control morphologies of self-assembled LCs inside a nanodroplet, a novel system that may find applications in nanofluidic devices or in photonic crystal technology.     

Fabrication and characterization of core-shell photonic crystals via a dipping process

High-quality polystyrene (PS) colloidal photonic crystals in large area were fabricated in 24 h via a capillary-enhanced process. Then, the photonic crystals with core-shell structure were obtained by incorporating silica nanoparticles into the interstitial space of opal template via a dipping process. The filling ratio (V_silica) of interstitial space could be manipulated by dipping colloidal crystals into suspensions with different concentrations of silica nanoparticles, which in turn renders the obtained core-shell photonic crystals. The absorptive peak of opal without dipping process is at 445 nm as measured by UV–vis spectrometry. The filling ratios of 0.130, 0.167 and 0.253 can be calculated according to the modified Bragg's Law, which corresponds to the absorptive peaks for core-shell opals at 453, 463 and 469 nm obtained from suspensions with silica nanoparticles of 0.017, 0.122, and 0.244 wt%, respectively. Therefore, by using this dipping process, the characteristic absorption wavelength for photonic crystal will be varied easily, efficiently and cost effectively than that by traditional methods for constructing opal from monodispersed colloids of different diameters.     

三维SiO2欧泊模板溶剂热法制备硫化锌光子晶体

以单分散二氧化硅微球在重力场下自组装得到的三维有序欧泊(opal)为模板，采用溶剂热法在模板空隙内生长ZnS晶体，从而制备高质量的硫化锌基光子晶体. 通过X射线衍射(XRD)和Raman光谱证明ZnS晶体为闪锌矿结构且晶体质量较好，并对其生长机理进行了讨论. 通过场发射扫描电子显微镜(FESEM)和紫外-可见分光光度计对所合成的ZnS/opal复合物与ZnS反欧泊结构进行了表征，结果表明两种结构都保持了欧泊三维有序性，并且在Г-L方向(垂直于(111)方向)上出现了布拉格衍射峰，说明其具有良好的光子晶体特性.