Mesoporous Silica Layer: Preparation and Opportunity

Periodic mesoporous silicas, which were prepared from silica‐surfactant mesostructured materials, have been investigated for a wide range of application due to their very large surface area, high porosity, pore size uniformity and variation, periodic pore arrangement and possible pore surface modification, after the pioneering papers on the formation of mesoporous silicas (MCM‐41 and FSM‐16). Morphosyntheses from such macroscopic morphologies as bulk monolith and film to nanoscopic ones, nanoparticles and their stable suspension, make mesoporous materials more attractive for applications and detailed characterization. Mesoporous silicas have been studied initially for such applications as adsorbent and catalyst, and more recently, optical, electronic, and bio‐related applications have been investigated. This review summarizes the studies on mesoporous silica film to highlight the present status and future of the preparation, characterization and application of the mesoporous silica film.     

改性中孔分子筛SBA-16薄膜的合成及表征

在酸性条件下, 以导电玻璃(ITO)为基底合成了SBA-16分子筛膜. 所制备的SBA-16膜孔径均匀, 具有体心立方结构(属于Im3m空间群), SBA-16膜的晶胞参数为18.6 nm. TEM, SEM和XRD等技术研究表明, 加入少量的AlCl₃盐于形成膜的母液并且采用RSiX₃对导电玻璃基底进行处理, 能够明显改善SBA-16膜的连续性而不影响孔结构. 红外(FTIR)研究结果表明, SBA-16膜的表面硅羟基和结晶水很少, 膜很稳定. XPS研究表明, 加入少量MnCl₂对SBA-16膜进行改性, 可以提高膜的导电性.     

介孔与介孔主客体材料在催化领域的应用

 综述了近年来介孔分子筛催化材料制备的研究成果及其在催化领域特别是精细化学品合成中的应用. 文章分为两部分,分别讨论了介孔材料本身作为催化剂以及介孔主客体催化材料的应用.     

非硅基介孔材料和介孔复合体的合成与特性

非硅基介孔材料和介孔复合体的合成与特性;介孔固体;介孔复合体;二氧化钛薄膜;液晶模板机理     

仿生介孔二氧化硅用于高效液相色谱拆分手性化合物

仿生介孔硅是以有机物作为模板,可有效复刻模板的独特形貌,从而得到其相同或相似结构孔径的介孔硅。本文从仿生的观点出发,从蟹壳中提取得到几丁质膜,将其用作模板制备了仿生手性向列型介孔二氧化硅,并用其制备了液相色谱柱,进行了手性化合物拆分实验。结果表明,该色谱固定相对10个手性化合物有一定的手性分离效果。     

Ordered Mesoporous Thin Films of Rutile TiO2 Nanocrystals Mixed with Amorphous Ta2O5

Ordered mesoporous thin films of composites of rutile TiO₂ nanocrystals with amorphous Ta₂O₅ are fabricated by evaporation‐induced self‐assembly followed by subsequent heat treatment beyond 780 °C. Incorporation of selected amounts of Ta₂O₅ (20 mol %) in the mesoporous TiO₂ film, together with the unique mesoporous structure itself, increased the onset of crystallization temperature which is high enough to ensure the crystallization of amorphous titania to rutile. The ordered mesoporous structure benefits from a block‐copolymer template, which stabilizes the mesostructure of the amorphous mixed oxides before crystallization. The surface and in‐depth composition analysis by X‐ray photoelectron spectroscopy suggests a homogeneous intermixing of the two oxides in the thin film. A detailed X‐ray absorption fine structure measurement on the composite film containing 20 mol % Ta₂O₅ and heated to 800 °C confirms the amorphous nature of the Ta₂O₅ phase. Photocatalytic activity evaluation suggests that the rutile nanocrystals in the synthesized ordered mesoporous thin film possess good ability to assist the photodegradation of rhodamine B in water under illumination by UV light.     

Thin Film of Mesoporous MCM-41 Grown on Indium-Tin-Oxide Glass Substrate

ThemesoporousM4lSmaterialshaveattractedconsiderableattentionsincetheywerefirstdiscoveredin19921'2.Thesematerials,amongwhichistheMCM-41molecularsievewithahexagonalarrayofmesopores(diameter15-100A),haveenormouspotentialinapplicationssuchascatalysis',host-guestchemistry"'andseparation'.UniformthinfilmsbasedonMCM-417-ichavealsobeenpreparedattheinterfacesofsolution/solidandair/solution.However,thepreviously-reportedfilmsweregrowninvariablyfromanacidicsolutioncontainingsurfactantmoleculesasthest…     

Stable Blue Luminescent CsPbBr3 Perovskite Nanocrystals Confined in Mesoporous Thin Films

Creating CsPbBr₃ perovskite nanocrystals with bright blue emission is challenging because their optical properties depend sensitively on structure. Growing perovskites in mesoporous templates bypasses some of these purification issues because the size of the nanocrystal is governed by the dimensions of the pores. Mesoporous silica consisting of aligned channels with tunable diameter can be easily synthesized and used as a template. When the perovskite solution evaporates and retreats, some of the liquid remains trapped in the interconnecting pores by discontinuous dewetting. The precursor crystallizes, generating stable ca. 3.1 nm blue‐emitting perovskite nanocrystals. The mesoporous template also serves as a protective barrier to preserve the optical properties of the CsPbBr₃ from atmospheric conditions. Compared to the bulk crystals and the powder composite, the strong blue‐shift of the emission peak in the film is accompanied by a decrease in the longer lifetime component and an 8‐fold increase in the external quantum efficiency.     

First Synthesis of Continuous Mesoporous Copper Films with Uniformly Sized Pores by Electrochemical Soft Templating

Although mesoporous metals have been synthesized by electrochemical methods, the possible compositions have been limited to noble metals (e.g., palladium, platinum, gold) and their alloys. Herein we describe the first fabrication of continuously mesoporous Cu films using polymeric micelles as soft templates to control the growth of Cu under sophisticated electrochemical conditions. Uniformly sized mesopores are evenly distributed over the entire film, and the pore walls are composed of highly crystalized Cu.     

中空纳米二氧化硅微球的制备及表征

本文介绍了一种制备中空纳米二氧化硅微球的新方法。利用模板首先合成介孔纳米二氧化硅微球,再用水热反应法,成功制备了非功能化和巯基、氨基功能化中空纳米二氧化硅微球。利用透射电子显微镜,热重分析等手段对其形貌进行了表征。另外,对中空介孔纳米二氧化硅微球的形成机制进行了探讨。     

介孔材料离子导电性的研究

介孔材料由于其奇特的性质和广泛的应用成为人们研究的热点。本文介绍了近几年来介孔材料质子和锂离子导电性的研究现状和发展趋势,主要总结了介孔纯氧化物、介孔纯氧化物的孔内修饰、介孔氧化物的孔壁掺杂修饰、介孔氧化物薄膜、介孔材料与有机高分子复合膜的离子导电性的研究进展。     

钛硅介孔分子筛

综述了钛硅介孔分子筛的合成、表征及其应用研究进展.评述了钛硅介孔分子筛的合成方法与合成条件对分子筛结构性能、钛物种的配位状态和催化性能的影响.介绍了鉴定钛硅介孔分子筛内骨架钛原子的多种波谱学方法以及钛硅介孔分子筛在选择氧化、光催化、酸催化反应中的应用,并指出钛硅介孔分子筛是一种非常有应用前景的环境友好的多相催化剂.     

Synthesis of Transparent Mesoporous and Mesostructured Thin Silica Films

A novel method for obtaining crack-free transparent periodic mesoporous thin films is described. Such films are prepared by a simple sol-gel process using surfactants as templates, with a pre-treatment of the glass substrate. The silicate precursor (tetraethoxysilane) is pre-hydrolyzed under acidic conditions before dissolving directly cetyltrimethylammonium bromide (CTAB). The solution is then spin-coated on pre-treated glass substrate. After the film has been deposited, it is calcined in air. X-ray Diffraction (XRD) has been used to characterize the film before and after thermal treatment. The film consists of a nanocomposite material with a periodic structure. Before calcination the XRD pattern has a sharp peak at d = 3.8 nms which is broadened and shifted by about 3.0 nm after calcination. Infrared transmission spectra have been performed on the films. Analysis of the free OH group stretching vibration indicates the removal of the surfactant after calcination in addition to an enhancement of the specific surface area.     

Synthesis of Mesoporous Platinum–Palladium Alloy Films by Electrochemical Plating in Aqueous Surfactant Solutions

Mesoporous platinum–palladium alloy films with different compositional ratios have been successfully synthesized by electrochemical plating in aqueous surfactant solutions. Scanning electron micrographs and transmission electron micrographs reveal that all of the platinum–palladium alloy films possess uniform mesopores with a narrow size distribution (around 7 nm). The alloy compositions in the pore walls can be controlled by changing the compositional ratios in the precursor solutions, as confirmed by inductively coupled plasma mass spectroscopy analysis and X‐ray photoelectron spectroscopy measurements. Due to large surface areas, the prepared mesoporous platinum–palladium films show distinctly enhanced electrocatalytic activity for methanol oxidation reactions, compared with the commercially available platinum black catalyst. Furthermore, compared with mesoporous platinum film, the alloying of platinum with palladium has a critical effect on the enhanced electrocatalytic activity. In particular, a mesoporous Pt₈₂–Pd₁₈ film exhibits highly enhanced electrocatalytic activity.     

介孔碳/聚苯胺修饰电极的制备及其对Cu~(2+)的响应研究(英文)

制备了一个新的电极-聚苯胺掺杂介孔碳修饰电极(PANI-MC),并且研究了电极的电化学性质。在介孔分子筛SBA-15的孔道中沉积蔗糖,然后在氮气的保护下,1200℃热裂解,生成孔道规则排列的介孔碳(MC);XRD、N2吸附-脱附、TEM等方法表征了介孔碳的结构,用SEM表征了PANI-MC修饰电极的形貌。结果表明:复合电极膜与修饰前的聚苯胺膜形貌不同,与介孔碳形貌相似,介孔碳纳米微粒的大小清洗可辨,长度大约为20~40μm。复合电极循环伏安结果显示:峰电位向负电位方向移动,这可能是因为介孔碳的孔道结构阻碍了离子的转移。同时,还研究了复合电极对Cu2+的相应,表明:电极对低浓度的Cu2+有很好的线性相应,可以作为Cu2+的感应器。     

有机-无机杂化氧化硅基介孔材料

有机基团可以通过嫁接或共聚的方法引入到氧化硅基介孔材料的孔表面或材料的骨架中,形成表面结合型和桥键型两大类有机-无机杂化氧化硅基介孔材料.本文综述了有机-无机杂化氧化硅基介孔材料的最新研究进展,介绍了其合成方法、应用及潜在的应用领域,详细总结了目前已报道的有机-无机杂化氧化硅基介孔材料的种类,展望了桥键型有机-无机杂化氧化硅基介孔材料的发展及应用前景.     

Ti-Si介孔分子筛的转晶与控制

以季铵盐型阳离子Gemini表面活性剂[C16H33(CH3)2N+(CH2)6N+(CH3)2C16H33]•2Br−(GEM16-6-16)为模板剂, 改变n(Ti)/n(Si)比值, 合成了系列Ti-Si介孔分子筛. X射线衍射(XRD)和透射电子显微镜(TEM)等表征结果表明, 在n(Ti)/n(Si)≤0.20时, 分子筛为高度有序六方介孔; 当 n(Ti)/n(Si)为 0.30时, 介孔转晶为立方相; 当n(Ti)/n(Si)为0.50时, 介孔转晶为层状相; n(Ti)/n(Si)为1.0时, 材料失去有序孔道结构. FT-IR分析表明, 在分子筛骨架间形成了Ti—O—Si键, 而且Ti—O—Si键的数目随n(Ti)/n(Si)的增加而增加, 达到一定饱和值后基本保持不变. 乙醇和丁醇对纯硅基介孔分子筛孔结构转晶控制作用呈现六方相→立方相→层状相递变规律, 因而钛酸正丁酯水解生成的丁醇对Ti-Si介孔分子筛转晶具有一定的控制作用.     

纳米介孔氧化铁的制备

纳米氧化铁的许多优异性能使其成为广泛的研究热点。本文介绍了纳米氧化铁的制备及其颗粒大小、形貌控制等方面的进展状况。综述了各种不同形态介孔氧化铁及含铁介孔纳米复合材料的研究进展,结合课题组的研究工作,重点评述了介孔氧化铁的制备进展,并对该领域的研究方向和需要解决的问题提出了自己的观点。     

Mesoporous Trimetallic PtPdRu Spheres as Superior Electrocatalysts

Mesoporous Trimetallic PtPdRu Spheres with well‐defined spherical morphology and uniformly sized pores were synthesized in an aqueous solution using ascorbic acid as the reducing agent and triblock copolymer F127 as the pore directing agent. These mesoporous PtPdRu spheres exhibited enhanced electrocatalytic activity compared to commercial Pt black, resulting in a ～4.9 times improvement in mass activity for the methanol oxidation reaction. The excellent electrocatalytic activity and stability are due to the unique mesoporous architecture and electronic landscape between different elements.     

A Mesoporous Superlattice Consisting of Alternately Stacking Interstitial Nanospace within Binary Silica Colloidal Crystals

A novel class of nonclassical structures of mesoporous silica, namely a binary nanoparticle mesoporous superlattice (BNMS), is obtained by the assembly of silica nanospheres of different sizes into a binary colloidal crystal. The colloidal crystal has a CrB‐type structure and consists of alternate stacks of unary fcc and binary AlB₂‐type structures along the b axis and has four types of interstitial mesopores. The BNMS can be deposited on a substrate by dip coating to form an oriented thin film in which the direction of the superstructure (b axis) is perpendicular to the substrate.