Fabrication of carbon fibers with nanoporous morphologies from electrospun polyacrylonitrile/poly(L‐lactide) blends

Porous carbon nanofibers were prepared through electrospinning a blend solution of polyacrylonitrile and poly(L ‐lactide), followed by carbonization at different temperatures and in different atmospheres. Structural features of these porous carbon nanofibers were characterized using scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, X‐ray powder diffraction, and Raman spectroscopy. Surface area and pore structure were evaluated using the nitrogen adsorption technique. It was found that carbon fibers prepared by this scalable and relatively economical method exhibited a porous surface morphology with high specific surface area and large pore volume. The fiber diameter, surface area, pore volume, bulky crystalline structure, and surface crystalline structure of these carbon nanofibers showed a strong dependence on the polymer precursor composition and carbonization condition. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 493–503, 2009     

生物质碳材料的孔道分析

生物质碳材料的孔道类型和孔径大小制约着材料有效的活性位点数量,影响材料的性能。孔道分类又是孔径分析的前提条件。因此,建立孔道分类的方法非常有意义。随着生物质碳材料的深入研究,研究者对其孔道分析的要求逐渐提高。他们用实际的吸脱附等温线与IUPAC规范中的吸脱附等温线进行匹配,来分类生物质碳材料的孔道。然而实际的吸脱附等温线具有不规则性,难以匹配IUPAC规范中的吸脱附等温线。所以,本文提出了孔隙率和比表面积占有率的孔道分类新方法。自制生物质碳材料,运用物理吸附仪和TEM (Transmission electron microscope)对其进行表征,采用BET方程（Brunauer-Emmett-Teller）、t-plot方法(Thickness-plot)、DFT方法（Non-local Density Functional Theory）、BJH（Barrett Joyner and Halenda）方法对其孔道进行分析。研究表明,采用孔隙率和比表面积占有率对其进孔道分类,可以准确的定义出微孔生物质碳材料、介孔生物质碳材料和微介孔生物质碳材料。本文用标准样品对孔隙率和比表面积占有率的孔道分类新方法进行论证,结果一致。因此,本文提出的孔隙率和比表面积占有率的孔道分类新方法准确可靠,实用性高。     

兼具高孔隙率和梯度孔隙结构的多孔钯块材的制备、表征及其电化学性能研究

钯材料广泛用于氢同位素储存和分离、催化和传感等领域.传统的负载钯催化材料具有优异的乙醇和甲醇等电化学催化氧化性能.除此之外,负载钯催化材料还具有优异的甲烷催化燃烧性能.然而,很多研究显示负载钯催化材料存在很多不足,例如在工程应用过程中不稳定,纳米颗粒会发生聚集和长大,进而引起材料性能急剧下降等.不同于钯片、海绵钯粉末和负载钯催化材料,多孔钯具有三维连通的孔隙结构,可避免团聚现象的发生.同时,多孔钯还具有一些特殊的物理化学性能.研究表明,梯度孔隙结构是一种高效的电化学催化结构.因而近年来很多研究者都致力于探索具有高孔隙率和梯度孔隙结构多孔钯块材的制备方法.已有的研究包括造孔剂法和模板法等,但上述方法制得的多孔钯块材均存在比表面积低或难以获得块体材料缺点.我们研究组发展了一种制备兼具高孔隙率和梯度孔隙结构的多孔钯块材的新方法.即通过以一定粒度的NaCl颗粒作为造孔剂放电等离子烧结制备PdAl合金复合块材,然后通过去离子水溶解获得多孔PdAl合金,最后经过在盐酸溶液中去合金化得到具有数十微米的宏观大孔和约10纳米的纳米孔等梯度孔隙结构的多孔钯块材.当造孔剂添加量为20 vol.%,制得了孔隙率高达88%且完整的多孔钯块材.对该多孔钯块材的力学性能进行了测试,其压缩强度为0.5 MPa.对该块材进行氮吸附测试,测试结果显示其比表面积达到54 m2/g.我们进一步对该多孔钯块材的乙醇电化学催化氧化性能进行了研究.对不同扫描速度下多孔钯块材在KOH(1 mol/L)+乙醇(0.8 mol/L)溶液中电催化活性进行分析.随着扫描速率从10 mV/s提高到50 mV/s,正扫描峰电流密度也逐渐提高,且峰电位向正电位方向移动.对峰电流密度和扫描速率的平方根进行拟合,发现它们之间存在明显的线性关系,表明该电催化氧化行为是一个受扩散控制的过程.随着溶液中乙醇浓度不断增加,正扫描方向乙醇氧化峰的峰电流呈现出先增大后减小的趋势.这是因为乙醇基和羟基在钯表面的竞争性吸附造成的.当乙醇浓度较高时,乙醇基会占据钯表面大量的活性位,从而阻碍和抑制羟基的吸附.此时,羟基在钯表面的吸附成为电氧化反应的控制因素.因此,只有选择合适的乙醇浓度,才能更好地发挥材料的电催化性能.当乙醇浓度为2 mol/L时,峰电流最大,达到120 mA/cm2,表明多孔钯块材具有优异的电催化性能,这与该材料的梯度孔隙结构、高比表面积和高孔隙率密切相关.进一步对多孔钯块材的催化稳定性进行研究.该多孔钯块材显示出了优异的催化稳定性,当经过50次循环后,乙醇氧化峰的峰电流仅下降到~110 mA/cm2.     

Synthesis of Fe3O4@poly(methylmethacrylate-co-divinylbenzene) magnetic porous microspheres and their application in the separation of phenol from aqueous solutions

A simple strategy to fabricate magnetic porous microspheres of Fe(3)O(4)@poly(methylmethacrylate-co-divinylbenzene) was demonstrated. The magnetic microspheres, consisting of polymer-coated iron oxide nanoparticles, were synthesized by the modified suspension polymerization of methacrylate and divinylbenzene in the presence of a magnetic fluid. The morphology and the properties of the magnetic porous microspheres were examined by scanning electron microscopy, transmission electron microscopy, superconducting quantum interference device, Fourier transform infrared spectroscopy, thermogravimetry, and X-ray powder diffraction. The pore size distribution and the specific surface area of the microspheres were measured by nitrogen sorption and mercury porosimetry technique. As predicted from the previous knowledge, the magnetic porous microspheres possessed a high specific surface area using n-hexane as a porogen. It was further found that the amounts of divinylbenzene and methacrylate, the ratio of porogens, and the dosage of ferrofluids affect the specific surface area of the microspheres. Furthermore, the microspheres were applied to remove phenol from aqueous solutions. The results showed that the microspheres had a high adsorption capacity for phenol and a high separation efficiency due to their porous structure, polar groups, and superparamagnetic characteristic.     

碳化硅衍生碳/球形天然石墨复合材料的制备及其结构调控

为满足储能领域对于材料兼具高能量密度和高功率密度的需求, 本文旨在将具有特殊孔隙结构的碳化物衍生碳与具有高导电性和高能量存储密度的石墨化碳(球形天然石墨)相复合, 制备得到一种多孔碳化硅衍生碳/球形天然石墨(SiC-CDCs@NG)复合材料. 采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、拉曼光谱、N₂吸/脱附等方法对材料的组成、结构、形貌、孔结构和比表面积等进行了表征. 结果表明,SiC-CDCs@NG材料具有较大的且可调节的比表面积和微孔体积, 微孔孔径集中在0.5-0.7 nm范围内; 通过改变NG/Si 摩尔比, 可以有效调控CDCs壳和NG核在复合材料中的组成分布、CDCs微孔的体积、孔径分布和比表面积.     

Mesoporous metal oxides by vapor infiltration and atomic layer deposition on ordered surfactant polymer films

Catalysis, chemical separations, and energy conversion devices often depend on well-defined mesoporous materials as supports or active component elements. Herein, we show that ordered assembled organic surfactant films can directly template porous inorganic solids with surface area exceeding 1000 m(2)/g by infusing the polymers with reactive inorganic vapors, followed by anneal. The specific surface area, pore size, chemical composition, and overall shape of the product material are tuned by choice of the polymer and precursor materials as well as the influsion and postinfusion treatment conditions. X-ray diffraction, infrared spectroscopy, and electron microscopy show that vapor infusion changes both the physical and chemical structure of the starting ordered polymer films, consistent with quantified trends in specific surface area and pore size distribution measured by nitrogen adsorption after film annealing. This method yields porous TiO(2) films, for example, that function as an anode layer in a dye-sensitized solar cell.     

Hierarchical porous carbon derived from Allium cepa for supercapacitors through direct carbonization method with the assist of calcium acetate

Hierarchical porous carbon was prepared from onion through a direct carbonization method and it was used as suercapacitor electrode material.     

Mesoporous hollow silicon spheres modified with manganese ion sieve: Preparation and its application for adsorption of lithium and rubidium ions

In this work, mesoporous hollow silicon spheres modified with 3‐aminopropyl‐ triethoxysilane (APTES) of loaded hydrogen manganese oxide lithium ion sieve (APTES/HMO‐ HS) was prepared. The structure and morphology of as‐prepared APTES/HMO‐HS were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, transmission electron microscopy and nitrogen adsorption‐desorption measurements. The Brunner‐Emmet‐Teller (BET) surface areas, pore diameters and pore volumes of APTES/HMO‐HS decreased gradually, while the Li:Mn:Si molar ratios range from 1:1:50 to 1:1:10. The obtained hierarchical porous APTES/50HMO‐HS has a high specific surface area (557.1694 m² g^‐1). The lithium and rubidium ions solutions were used to measure the adsorption performance of the APTES/HMO‐HS adsorbent. The pseudo‐first‐order and pseudo‐second‐order kinetics, Langmuir and Freundlich isotherms of APTES/HMO‐HS were investigated; suggesting that the adsorption kinetics can be described by the pseudo‐second‐order kinetic model and the adsorption isotherms well fits the Langmuir isotherm equation. The obtained results show that the prepared APTES/HMO‐HS exhibits excellent abilities to simultaneously and selectively recover Li⁺ and Rb⁺ (11.22 mg·g^‐1 and 8.31 mg·g^‐1) and have a promising application in the simultaneous adsorption of lithium and rubidium ions.     

Surface characterization and heats of adsorption of chromatographic alumina gel

The porous nature of chromatographic alumina gel has been investigated by adsorption/condensation processes and electron microscopy. Having 63% porosity, the gel is very porous. Total pore volume as determined by the fluid-displacement method is 0.497 cm³ g^–1. Its specific surface area, as determined by water vapor adsorption, is 225 m² g^–1. Micropore volume, as determined by utilizing Gurwitsch's rule, turns out to be 0.262 cm³ g^–1. The greater portion of the surface area and pore volume occurs in small and transitional pores, with average pore radii (hydraulic) less than 2.1 nm.Organic vapors, such as methyl ethyl ketone, acetone, methyl acetate, and methyl alcohol, were adsorbed on the gel between 0 and 36°C under vacuum, and the data were recorded on a Cahn-1000 electrobalance device. Isosteric heats of adsorption were calculated by applying the Clausius Clapeyron equation to the adsorption isosters at different surface coverages. Two types of adsorption processes, one with low activation energy and other with high activation energy can be distinguished. The increase in values ofq _st indicates that increasing temperature changes physical adsorption into chemisorption.     

Preparation of different graphene nanostructures for hydrogen adsorption

In this study, different types of graphene were synthesized to investigate hydrogen adsorption capacity at different pressures (0–34 bar) at room temperature (298 K). Graphene and nanoporous graphene were prepared by Chemical Vapor Deposition (CVD) method, using methane as a carbon source at a temperature of 900 °C over copper plates and nickel oxide nanocatalyst. The nickel oxide nanocatalyst was prepared by sol–gel method, whereas graphene oxide was prepared through modified Hummer's method. The products were characterized by X‐ray diffraction, field emission‐scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller and Raman spectroscopy. The adsorption of hydrogen was done by volumetric method. High adsorption capacity was achieved in nanoporous graphene because of its high pore volume (2.11 cm³/g) and large specific surface area (850 m²/g). Hydrogen adsorption values for nanoporous graphene, graphene and graphene oxide were determined as 2.56, 1.70 and 0.74 wt%, respectively. In addition, the hydrogen adsorption of graphene nanostructures fitted nicely to the selected two‐parameter and three‐parameter adsorption isotherm models. The adsorption isotherm model coefficients have been found for a 0–34 bar pressure range. The parameter values for all adsorbents showed proper conformity to the model and experimental data. Copyright © 2016 John Wiley & Sons, Ltd.     

Investigation of the porosity of silica and alumina with chemically bonded polystyrene

The effect of modification of porous silica and alumina with a copolymer of styrene and vinylsilane on the porosity of oxides have been investigated by means of low temperature nitrogen sorption. Only small changes of the specific surface area and of the specific pore volume were observed on modification of oxides with non-cross-linked copolymer. The specific surface area significantly increased after the cross-linking of the deposited polymeric layer while the specific pore volume remains almost unaffected. A broad hysteresis loop appears in the nitrogen sorption isotherm for the alumina modified with the cross-linked polymer. The porosity of oxides modified by chemisorption method differed strongly from that observed for composites modified by physisorption of polymer.     

Calix[4]arenes functionalized dual‐imprinted mesoporous film for the simultaneous selective recovery of lithium and rubidium

Calixarenes have been drawing tremendous interest due to their special structure, superior properties and numerous applications. In this work, a novel adsorbent material, calix[4]arenes functionalized dual‐imprinted mesoporous film (DIMFs) for the simultaneous selective recovery of Li(I) and Rb(I), was prepared via surface ionic imprinting. Compared with ordinary adsorbent materials, the synthesis process of the films used a cheap bio‐template and did not require extra steps but significantly enhances adsorption properties. The morphology and structure of prepared DIMFs were characterized by scanning electron microscopy, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT‐IR) and nitrogen adsorption–desorption measurements. Adsorption parameters (pH and temperature), adsorption kinetics and adsorption isotherms of the DIMFs were investigated by adsorption experiments. This novel adsorbent has inorganic–organic hybrid frameworks, high specific surface area and uniform pore size. The Langmuir and Freundlich isotherms, pseudo‐first‐order and pseudo‐second‐order kinetics of DIMFs were investigated; suggesting that the adsorption data well fits the Langmuir isotherm model, and the adsorption kinetics can be described by the pseudo‐second‐order kinetic model. In addition, dual‐imprinted mesoporous film exhibited superior selectivity for Li(I) and Rb(I). Cycle test demonstrated an outstanding of reusability, which appreciating their potential for industrial application.     

活性炭纤维孔结构控制和表面改性

活性炭纤维（ACF-ActivatedCarbonFiber）是本世纪七十年代发展起来的纤维状吸附剂[1]。其吸附性能与表面积、细孔直径、细孔分布等物理结构密切相关，同时与其表面化学结构密不可分，本文综述介绍ACF的孔结构控制方法和表面化学改性与吸附性能的关系。     

Surfactant‐directed one‐pot preparation of novel Ti‐containing mesomaterial with improved catalytic activity and reusability

Titanium was incorporated in ionic liquid based periodic mesoporous organosilica to prepare a nanostructured catalyst (Ti@PMO‐IL) with high activity. Procedure for the synthesis of Ti@PMO‐IL was followed according the simultaneous hydrolysis and condensation of alkylimidazolium ionic liquid, tetramethoxysilane (TMOS) and tetrabutylorthotitanate (TBOT) where a surfactant template was used together with a simple acid‐based catalytic aproach. N₂ adsorption isotherm of the Ti@PMO‐IL was studied to measure its mean pore volume, pore size distribution and specific surface area. Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy was applied to identify the chemical bonds present in Ti@PMO‐IL. The morphology of this nanomaterial was investigated by scanning electron microscopy (SEM). Transmission electron microscopy (TEM) image was used to study mesoporosity and structure order of the catalyst. The catalytic activity of Ti@PMO‐IL was then studied and found to be efficient and reusable to catalyze Hantzsch reaction.     

On the mechanism of nanopore filling of SAPO-5 molecular sieve by nitrogen molecules

SAPO-5 molecular sieve was synthesized according to patent literature and characterized with X-ray diffraction, electron microscopy (SEM, TEM), and solid state magic angle spinning NMR spectroscopy. The material of particles in the micrometer region was found to consist of ca. 20 nm microcrystallites packed in mostly parallel orientation to ca. 200 nm sized agglomerates. The nitrogen adsorption isotherm was measured at 77.6 K over ca. 7 decades of pressure up to pore saturation. The course of the isotherm is interpreted to consist of filling of the nanopores (diameter, 0.73 nm) up to 2N(2)/unit cell, subsequent multilayer adsorption on the outer surface of the agglomerates, and, finally, pore condensation in the interparticle adsorption space. The nanopore adsorption can be quantitatively reproduced with the statistical mechanical model of a quasi one-dimensional lattice gas taking intermolecular interactions into account. The evaluated energy parameters are of physically reasonable magnitude and agree with literature data. The multilayer part of the adsorption isotherm can be well represented by the Brunauer-Emmett-Teller model yielding a specific outer space area (63 m(2) g(-)(1)) which is consistent with estimated geometrical and pore size analysis data.     

Development of immobilization technique for liver microsomes

In the present report, physically adsorbed rat liver microsomes were used in order to optimize the immobilization of membrane proteins on solid surfaces for use in biosensing and microreactor applications. Physical adsorption was used to form thin films on solid supports (gold, mica, macroporous aluminum oxide membrane). The characterization of the films was performed by surface plasmon resonance (SPR), atomic force microscopy (AFM) and environmental scanning electron microscopy (ESEM). Commercially available macroporous aluminium oxide membranes with a high surface area, allow the retention of a high amount of microsomal membranes in the form of a thin film. Microsomal film functionality was tested by monitoring the activities of several enzymes of phases I and II. Microsomal modified supports can be re-utilized for the same or different substrate after washing with appropriate buffer.     

液相渗硅法制备多孔Si/SiC生物形态陶瓷

榉木经高温热解转化为碳模板,通过液相渗硅反应（LSIP）,在1550℃,1.5h渗硅,1700℃排硅制备了保持木材微观结构的多孔Si/SiC陶瓷。利用X-射线衍射分析（XRD）, 扫描电子显微镜（SEM）,压汞技术对样品的物相构成、显微结构和孔径分布进行了分析,利用阿基米德法和三点弯曲法测定了多孔陶瓷的显气孔率、密度和弯曲强度。结果表明,最终产物由主晶相β-SiC和少量的Si组成;控制高温排硅时间可以得到孔隙率为16％~32％的多孔Si/SiC陶瓷,可调控其产物的相组成和力学性能。对LSIP工艺的反应机理进行了探讨。     

A new approach to nickel electrolytic colouring of anodised aluminium

Energy dispersive X-ray spectroscopy and scanning electron microscopy were used to analyse nickel on anodic aluminium surfaces after stripping the anodic aluminium oxide. The metal was electroplated at the bottom of the pores of anodised aluminium during electrolytic colouring in solutions without (Watts) and with (citrate) complexing agents, respectively. A relation between the anodic-cathodic processes, changes of the structure and composition of the coating in dependence on the used solution were studied. A morphology study performed after stripping the anodic aluminium oxide revealed the crucial influence of the anodic process/cycle and the complexing agent on the nickel structure on the aluminium surface. Off-time of half-way rectified current influenced the nickel deposition in the pores of anodic alumina negatively.     

医用多孔壳聚糖膜的制备及性能研究

以邻苯二甲酸二丁酯为致孔剂,制备了多孔壳聚糖膜,并用扫描电镜对其表面和断面形貌进行了分析,同时对膜的吸水性、水蒸气透过性、比表面积、力学性能及生物相容性等进行了考察。分析结果表明:以邻苯二甲酸二丁酯为致孔剂,制备的多孔壳聚糖膜孔径均匀,吸水性好,孔隙率高,比表面积大,膜的最大吸水率、孔隙率和比表面积分别为196%、71.5%和1.0472 m2.g-1;膜的力学性能好,最大抗拉强度为273.17MN/m2。