Amphiphilic Organic–Inorganic Hybrid Zeotype Aluminosilicate like a Nanoporous Crystallized Langmuir–Blodgett Film

A new organic–inorganic hybrid zeotype compound with amphiphilic one‐dimensional nanopore and aluminosilicate composition was developed. The framework structure is composed of double aluminosilicate layers and 12‐ring nanopores; a hydrophilic layer pillared by Q² silicon atom species and a lipophilic layer pillared by phenylene groups are alternately stacked, and 12‐ring nanopores perpendicularly penetrate the layers. The framework topology looks similar to that of an AFI‐type zeolite but possesses a quasi‐multidimensional pore structure consisting of a 12‐ring channel and intersecting small pores equivalent to 8‐rings. The hybrid material with alternately laminated lipophilic and hydrophilic nanospaces can be assumed as a crystallized Langmuir–Blodgett film. It demonstrates microporous adsorption for both hydrophilic and lipophilic adsorptives, and its outer surface tightly adsorbs lysozyme whose molecular size is much larger than its micropore opening. Our results suggest the possibility of designing porous adsorbent with high amphipathicity.     

Porous structure of the catalyst layers of electrodes in a proton-exchange membrane fuel cell: A stage-by-stage study

Porous structure is studied by standard contact porosimetry after each stage in the preparation of a catalyst layer, which contains a carbon substrate (CS), an ionomer in the form of Nafion resin, and a platinum catalyst. The influence of the ionomer on the porous structure of ten different CS is investigated. The structure of these samples is studied over the maximum range of their pore radii r ∼ 0.3–10⁵ nm. Pores of main volume within particles of the CS under investigation are mainly distributed over the maximum range of their radii from r ≤ 1 to ∼ 50 nm. Ionomer introduction into all the CS under investigation leads to an increase in the integral porosity due to the porosity of the intergranular structure. The change in porosity of the intragranular structure is caused by ionomer blocking small pores in the CS. In most CS, ionomer blocks pores of different sizes, from micropores with radii r ≤ 1 nm and up to r ∼ 1000 nm. It is concluded that the extent of blockage of CS pores is largely determined by the surface properties of the CS and Nafion resin and, more precisely, by the difference in resin adhesion to the CS surface because of the presence of different surface groups on the CS surface. When platinum is applied to CS, this leads to an increase in the specific volume of the micropores. The smallest dimensions of platinum particles are estimated to be on the order of 1 nm.     

Synthesis of High‐Surface‐Area Nitrogen‐Doped Porous Carbon Microflowers and Their Efficient Carbon Dioxide Capture Performance

Sustainable carbon materials have received particular attention in CO₂ capture and storage owing to their abundant pore structures and controllable pore parameters. Here, we report high‐surface‐area hierarchically porous N‐doped carbon microflowers, which were assembled from porous nanosheets by a three‐step route: soft‐template‐assisted self‐assembly, thermal decomposition, and KOH activation. The hydrazine hydrate used in our experiment serves as not only a nitrogen source, but also a structure‐directing agent. The activation process was carried out under low (KOH/carbon=2), mild (KOH/carbon=4) and severe (KOH/carbon=6) activation conditions. The mild activated N‐doped carbon microflowers (A‐NCF‐4) have a hierarchically porous structure, high specific surface area (2309 m² g^?1), desirable micropore size below 1 nm, and importantly large micropore volume (0.95 cm³ g^?1). The remarkably high CO₂ adsorption capacities of 6.52 and 19.32 mmol g^?1 were achieved with this sample at 0 °C (273 K) and two pressures, 1 bar and 20 bar, respectively. Furthermore, this sample also exhibits excellent stability during cyclic operations and good separation selectivity for CO₂ over N₂.     

煤焦气化过程中比表面积和孔容积变化规律及其影响因素研究

煤焦的孔隙结构是影响气化反应的重要因素之一，本文通过测定部分气化焦样的比表面积及其孔隙结构，详细地研究了烟煤焦的孔隙结构在气化过程中的变化规律及其影响因素，结果表明，煤焦的孔隙结构在气化过程中的变化不但取决于原煤的性质，而且还取决于气化介质与气化温度；在相同条件下气化至相同气化率时总比表面积和孔体积大小顺序为彬县＞神木＞王封煤焦，总比表面积与微孔比表面积均随温度的升高而降低，在反应的前期CO2与H2O两种气氛下产生的总比表面积与微孔比表面积相当，但在反应后期CO2气氛下能够产生更多的总比表面积与微孔比表面积。     

石油焦水蒸气气化过程孔隙结构和气化速率的变化

以氮气为吸附质，测定了部分气化石油焦的比表面积、孔容及其随孔径的分布，研究了石油焦的孔隙结构在气化过程中的变化及其对气化反应的影响。结果表明，石油焦的孔主要由微孔组成；水蒸气条件下气化时石油焦的比表面积、孔容随碳转化率增加而不断增大；不同孔隙率和比表面积的石油焦，其气化反应速率曲线变化趋势不同；石油焦的比气化反应速率与孔隙结构有着紧密的关系，比气化反应速率和有效比表面积之间有着较好的线性关系。     

Controllable Synthesis of Mesoporous Iron Oxide Nanoparticle Assemblies for Chemoselective Catalytic Reduction of Nitroarenes

Iron(III) oxide is a low‐cost material with applications ranging from electronics to magnetism, and catalysis. Recent efforts have targeted new nanostructured forms of Fe₂O₃ with high surface area‐to‐volume ratio and large pore volume. Herein, the synthesis of 3D mesoporous networks consisting of 4–5 nm γ‐Fe₂O₃ nanoparticles by a polymer‐assisted aggregating self‐assembly method is reported. Iron oxide assemblies obtained from the hybrid networks after heat treatment have an open‐pore structure with high surface area (up to 167 m² g^?1) and uniform pores (ca. 6.3 nm). The constituent iron oxide nanocrystals can undergo controllable phase transition from γ‐Fe₂O₃ to α‐Fe₂O₃ and to Fe₃O₄ under different annealing conditions while maintaining the 3D structure and open porosity. These new ensemble structures exhibit high catalytic activity and stability for the selective reduction of aryl and alkyl nitro compounds to the corresponding aryl amines and oximes, even in large‐scale synthesis.     

Polymer‐Derived Silicoboron Carbonitride Foams for CO2 Capture: From Design to Application as Scaffolds for the in Situ Growth of Metal–Organic Frameworks

A template‐assisted polymer‐derived ceramic route is investigated for preparing a series of silicoboron carbonitride (Si/B/C/N) foams with a hierarchical pore size distribution and tailorable interconnected porosity. A boron‐modified polycarbosilazane was selected to impregnate monolithic silica and carbonaceous templates and form after pyrolysis and template removal Si/B/C/N foams. By changing the hard template nature and controlling the quantity of polymer to be impregnated, controlled micropore/macropore distributions with mesoscopic cell windows are generated. Specific surface areas from 29 to 239 m² g^?1 and porosities from 51 to 77 % are achieved. These foams combine a low density with a thermal insulation and a relatively good thermostructural stability. Their particular structure allowed the in situ growth of metal–organic frameworks (MOFs) directly within the open‐cell structure. MOFs offered a microporosity feature to the resulting Si/B/C/N@MOF composite foams that allowed increasing the specific surface area to provide CO₂ uptake of 2.2 %.     

On a Simple Nonisothermal Adsorption Experiment with Organic Vapors and an Inertial Microbalance To Study the Surface Properties of Hybrid (Organic/Inorganic) Porous Materials

A nonisothermal adsorption experiment using a controlled flow of cyclopentane in the 333-313 K range is used to simultaneously estimate the specific surface area and micropore volume of a hybrid (organic/inorganic) alcogel. For reference, the method is also applied to an all-inorganic material with a more rigid structure, namely, a high surface area SiO(2)-Al(2)O(3). The proposed data analysis provides guidelines to determine whether adsorption data on a certain adsorbate/adsorbent system can be modeled effectively as a convolution of BET (meso- and macropore) and Dubinin-Radushkevitch (DR, micropore) contributions. Copyright 2000 Academic Press.     

孔结构对活性炭吸附水溶液中铅离子的影响

选取三种表面化学性质相近的活性炭(AC),通过等温吸附实验考察活性炭对水溶液中铅离子的吸附性能,利用扫描电子显微镜(SEM)观察活性炭的表面微观形貌,通过低温(77 K)液氮吸附测定活性炭的比表面积和孔容,并分别以密度泛函理论(DFT)和Barrett-Joyner-Halenda (BJH)法计算微孔和中孔的孔径分布.结果表明:选用的三种活性炭AC1、AC2、AC3在比表面积和总孔容上呈依次下降的趋势,但表面开放孔均匀分布的AC2,具有最高的饱和吸附量,孔结构类似颗粒堆积孔的AC3,具有与表面开放孔分布集中的AC1相近的饱和吸附量;通过对孔结构与吸附量的关联分析可知,在活性炭吸附铅离子的过程中, 0.4-0.6 nm的孔是有效吸附孔, 10.5-20.6 nm、20.6-55.6 nm、5.2-10.5 nm三个区间的孔则会对吸附产生阻碍作用.     

黏合剂对其ZSM-5分子筛成型物裂解石脑油的影响

为考察成型时,黏合剂性能对ZSM-5分子筛的影响,对同一分子筛用六种不同黏合剂捏合,挤条成型,进行SEM、NH₃-TPD和N₂物理吸附表征。结果表明,六个成型物在形貌和BET比表面积均无明显差异,二次孔数量明显比分子筛原粉增加。所用纯硅溶胶黏合剂的成型物,其NH₃-TPD酸量、微孔体积和微孔比表面积低于其分子筛原粉。所用含铝黏合剂的成型物,其NH₃-TPD酸量、微孔体积和微孔比表面积变化不明显,BJH累积孔体积明显增加。在固定床反应器中于600 ℃裂解石脑油。发现,纯硅溶胶黏合剂成型物的乙烯+丙烯收率明显低于含铝黏合剂。     

高温下煤焦的碳微晶及孔结构的演变行为

以贵州煤为原料,在热解温度950℃~1400℃制备了各种慢速和快速热解焦,主要对高温热解过程中煤焦的碳微晶和孔结构的演变行为进行了研究,同时也研究了高温气化过程中煤焦的孔结构变化规律。结果表明,慢速热解焦和快速热解焦的C和H含量明显不同;随热解温度的升高,煤焦的碳微晶结构向有序化方向发展,但慢速热解煤焦比快速热解煤焦的"石墨化"程度大;快速热解煤焦的微孔比表面积和微孔容积明显高于慢速热解煤焦,即快速热解煤焦的孔隙结构明显比慢速热解煤焦发达;在气化反应初期,煤焦的微孔比表面积下降,微中孔比表面积增加,反应后期煤焦的总比表面积快速下降。     

Effects of fluorination modification on pore size controlled electrospun activated carbon fibers for high capacity methane storage

Electrospun carbon fibers were prepared as a methane storage medium. Chemical activation was carried out using potassium carbonate to develop the pore structure, which can provide sites for the uptake of methane, and then fluorination surface modification was conducted to enhance the capacity of storage. Chemical activation provided a highly microporous structure, which is beneficial for methane storage, with a high specific surface area greater than 2500 m²/g. The pore size distribution showed that the prepared samples have pore sizes in the range of 0.7–1.6 nm. The effect of fluorination surface modification was also investigated. The functional groups, which were confirmed by XPS analysis, played an important role in guiding methane gas into the carbon silt pores via the attractive force felt by the electrons in the methane molecules due to the high electronegativity of fluorine. Eventually, the methane uptake increased up to 18.1 wt.% by the synergetic effects of the highly developed micropore structure and the guiding of methane to carbon pores by fluorine.     

介孔二氧化锆分子筛比表面和孔结构的调变

在非离子表面活性剂PEO作用下，用固态反应结构导向法合成了介孔二氧化锆。根据Zr-O-Zr骨架结构与有机物种键合较弱的特点，使用了溶剂抽提法脱除结构导向剂。结果发现该法所得介孔材料与焙烧法所得结构显著不同，溶剂抽提法所得材料具有丰富的介孔结构，且比表面较高；而焙烧法所得样品为超微孔结构，热稳定性较高，SEM结果表明在较高的焙烧温度下其有序的表观形貌依然存在。     

High surface area nanoporous amorphous silica prepared by dodecanol assisted silica formate sol-gel approach

A simple polycondensation of monocarboxylic acids with silicon alkoxides led to transparent silica gels mainly comprised of silicate species of closed structures. This 'sol-gel formic acid' approach was modified by trapping an organic template (dodecanol) inside the silicate network during the polymerization process. Using this templating approach, porous silica of extremely high surface area, was produced in contrast to non-porous silica obtained by non-templating approach. The S(BET) surface areas of the template assisted samples resulting from the entire pores were found to be up to 725 m(2)/g. The total pore volumes of the samples were in the range of 0.40-0.74 cc/g in which micropore volumes were about 0.15-0.25 cc/g; the porosity depending on the reactants molar ratios of dodecanol, silicon alkoxide and formic acid.     

Enhanced hydrogen storage capacity of high surface area zeolite-like carbon materials

We report the synthesis of zeolite-like carbon materials that exhibit well-resolved powder XRD patterns and very high surface area. The zeolite-like carbons are prepared via chemical vapor deposition (CVD) at 800 or 850 degrees C using zeolite beta as solid template and acetonitrile as carbon precursor. The zeolite-like structural ordering of the carbon materials is indicated by powder XRD patterns with at least two well-resolved diffraction peaks and TEM images that reveal well-ordered micropore channels. The carbons possess surface area of up to 3200 m2/g and pore volume of up to 2.41 cm3/g. A significant proportion of the porosity in the carbons (up to 76% and 56% for surface area and pore volume, respectively) is from micropores. Both TEM and nitrogen sorption data indicate that porosity is dominated by pores of size 0.6-0.8 nm. The carbon materials exhibit enhanced (and reversible) hydrogen storage capacity, with measured uptake of up to 6.9 wt % and estimated maximum of 8.33 wt % at -196 degrees C and 20 bar. At 1 bar, hydrogen uptake capacity as high as 2.6 wt % is achieved. Isosteric heat of adsorption of 8.2 kJ/mol indicates a favorable interaction between hydrogen and the surface of the carbons. The hydrogen uptake capacity observed for the zeolite-like carbon materials is among the highest ever reported for carbon (activated carbon, mesoporous carbon, CNTs) or any other (MOFs, zeolites) porous material.     

甲烷在活性炭上裂解制氢研究

在连续流动石英固定床反应器上研究了甲烷在活性炭上裂解制氢的反应，并对反应前后活性炭的比表面积以及孔径分布等的变化进行了测定。结果表明，甲烷在五种活性炭上的裂解行为基本相同，反应初期转化率最高，随着反应进行转化率逐渐降低直至一个平稳的状态；降低甲烷分压和增加甲烷与活性炭的接触时间可提高甲烷转化率；温度的升高有利于初始转化率的提高，但不利于活性炭的稳定性；反应后活性炭比表面积、孔容及微孔孔容都明显降低，平均孔径增大，孔径分布向中孔方向迁移，说明甲烷的裂解导致了活性炭孔特别是微孔内的炭沉积以及进一步的孔堵塞。     

Hydrogen adsorption in transition metal carbon nano-structures

Templated microporous carbons were synthesized from metal impregnated zeolite Y templates. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to characterize morphology and structure of the generated carbon materials. The surface area, micro- and meso-pore volumes, as well as the pore size distribution of all the carbon materials were determined by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. All the hydrogen adsorption isotherms were Type 1 and reversible, indicating physisorption at 77 K. Most templated carbons show good hydrogen storage with the best sample Rh-C having surface area 1817 m²/g and micropore volume 1.04 cm³/g, achieving the highest as 8.8 mmol/g hydrogen storage capacity at 77 K, 1 bar. Comparison between activated carbons and synthesized templated carbons revealed that the hydrogen adsorption in the latter carbon samples occurs mainly by pore filling and smaller pores of sizes around 6 Å to 8 Å are filled initially, followed by larger micropores. Overall, hydrogen adsorption was found to be dependent on the micropore volume as well as the pore-size, larger micropore volumes showing higher hydrogen adsorption capacity.     

Quantification of the pore size distribution (porosity profiles) in microfiltration membranes by SEM,TEM and computer image analysis

Transport properties of membranes are closely related to morphological properties like surface porosity and variation of their inner pore structure. Scanning electron microscopy (SEM) as well as transmission electron microscopy (TEM) are powerful tools to characterise the microscopical pore structure of membranes in a qualitative manner. In order to provide more quantitative data of surface and cross-sectional pores computer image analysis can be used. Parameters like ‘porous area fraction’ and ‘mean free path length’ have been selected to describe the pore distribution within porosity profiles in order to consider the effect that the pores within the cross-section are connected to each other.     

Synthesis and adsorption properties of gold nanoparticles within pores of surface‐functional porous polymer microspheres

Mesoporous polymer microspheres with gold (Au) nanoparticles inside their pores were prepared considering their surface functionality and porosity. The Au/polymer composite microspheres prepared were characterized by transmission electron microscope (TEM), X‐ray diffraction (XRD), and Brunauer–Emmett–Teller (BET) techniques. The results showed that the adsorption of Au nanoparticles could be increased by imparting the pore structure and surface‐functional groups into the supporting polymer microspheres (in this study, poly (ethylene glycol dimethacrylate‐co‐acrylonitrile) and poly (EGDMA‐co‐AN) system). Above all, from this study, it was established that the porosity of the polymer microspheres is the most important factor that determines the distribution and adsorption amount of face‐centered cubic (fcc) Au nanoparticles in the final products. Our study showed that the continuous adsorption of Au nanoparticles with the aid of the large surface area and surface interaction sites formed more favorably the Au/polymer composite microspheres. The BET measurements of Au/poly(EGDMA‐co‐AN) composite microspheres reveals that the adsorption of Au nanoparticles into the pores kept the pore structure intact and made it more porous. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5627–5635, 2004     

Evaluation of the porous structures of new polymer packing materials by inverse size-exclusion chromatography

A highly cross-linked porous polymer resin based on styrene-divinylbenzene matrix with pores created by the use of micellar imprinting technique was used as chromatographic packing material. Its performance as a column packing material in inverse size-exclusion chromatography was compared with a non-imprinted resin of the same polymer matrix. The porous structures (the pore size and the porosity) of the resins in the dry and wet states and their relationships with the elution volume of probe solutes (alkanes and polystyrene standards) were established. Characteristic properties of the resins such as specific pore volume, specific surface area and porosity are compared with results obtained by other methods of characterization such as mercury intrusion porosimetry, solvent regain and nitrogen sorption. The results show that the new porous resin can be used in the separation of small molecules. The separation is based on the size of the molecules, and the larger pores (meso- and macropores) in the porous resin can provide a much easier access to the smaller pores (micropores) which are useful in the chromatographic separations.