超级电容器炭电极材料孔结构对其性能的影响

采用无瓶颈的系列酚醛树脂活性炭为电极材料，用氮吸附和恒流充、放电，以及交流阻抗法，研究孔径和孔表面积等孔结构对其性能的影响.结果表明，活性炭电极材料双电层电容与微孔(孔宽度< 2.0 nm)表面和外孔(孔宽度 >2.0 nm)表面都有关系，但主要取决于微孔表面双电层电容.微孔表面比电容为21.4 μF•cm－2，外孔表面比电容< 10 μF•cm－2.外孔表面比电容较低可能是由于空间电荷层的影响.微孔孔径较大的炭材料具有高比电容和良好的高倍率放电的特性.     

Characterization of ignition and combustion characteristics of phenolic fiber-reinforced plastic with different thicknesses

The present study focuses on ignition and combustion characteristics of phenolic fiber-reinforced plastic (FRP) with different thicknesses under different external heat fluxes using cone calorimeter, which receives little attention to date. A series of parameters including ignition time, thermal thickness, mass loss factor, mass loss rate (MLR), heat release rate (HRR), total heat release (THR), fire performance index (FPI) and fire growth index (FGI) are measured or calculated. Results indicate that the ignition time increases with the thickness, but decreases with the external heat flux. Phenolic FRP with thickness of 3 mm may be considered as thermally thin material. However, phenolic FRP with thickness of 5 and 8 mm is prone to be thermally thick material. The critical heat flux, minimum heat flux and ignition temperature are deduced and validated. The thermal thickness increases with the external heat flux. Linear correlations of the thermal thickness with the ratio of specimen density and external heat flux are demonstrated and presented. The mass loss factor decreases with the thickness. Three and two peak MLRs occur in the cases of low and high external heat fluxes, respectively. The average MLR increases with the external heat flux and thickness. The average and maximum HRR increases with the external heat flux. The FGI for the maximum HRR increases with the external heat flux. Linear correlations of the average MLR, the average and maximum HRR and the FGI for the maximum HRR with the external heat flux are demonstrated and presented.

     

Effect of poly(ethylene glycol) 200 on the formation of a polyetherimide asymmetric membrane and its performance in aqueous solvent mixture permeation

To investigate the effect of poly(ethylene glycol) (PEG) 200 on membrane performance, asymmetric polyetherimide (PEI) membranes with a small pore size were prepared by dry/wet-phase inversion from the casting solution containing N-methyl-2-pyrrolidone as a solvent and poly(ethylene glycol) 200 as an additive. Our experiment revealed that the addition of PEG 200 has an influence on the casting solution properties, permeation properties, and resulting membrane structures. Moreover, a drying process also affects the formation of a dense skin layer. Increasing the amount of PEG 200 drastically improved the solute rejection rate. The drying process improved the rejection rate. We also observed the effect of the mixed solvent (water/ethanol) on permeation through the membranes with various pore sizes. In the case of the membrane with a dense skin layer, the solvent permeation showed relationships with solution viscosity, surface tension, and membrane-solvent interaction.     

Probing microstructure evolution during the hardening of gypsum by proton NMR relaxometry

We report a comprehensive proton NMR relaxation study of the water confined in the evolving porous structure of hardened gypsum prepared with different water-to-plaster ratios (w/p) and increasing additions of crushed gypsum. This study gives some new information on the microstructure, the water distribution, and the hydration kinetics without any drying or perturbing preparation. The bi-exponential transverse magnetization decay reveals the existence of two water populations in slow exchange. However, the different behaviors of these populations during saturation and desaturation experiments show evidence of a fast exchange of each population with the surface. Two modes of organization of the microstructure of this material are identified through an original model of exchange as a function of the water-to-plaster ratio (0.4 < or = w/p < or = 0.6 and 0.7 < or = w/p < or = 1). A clear gap is shown in the exchange rate value above w/p = 0.6 that could be representative of a percolation threshold. Both the method and the theory presented can be applied more widely to other porous media with reactive surface areas.     

Drying and nondrying layer-by-layer assembly for the fabrication of sodium silicate/TiO2 nanoparticle composite films

Influences of drying and nondrying steps on structures of layer-by-layer (LbL) assembled sodium silicate/TiO(2) nanoparticles films (donated as silicate/TiO(2) films) have been systematically investigated. The nondrying LbL assembly produces highly porous silicate/TiO(2) films with large thickness. In contrast, the silicate/TiO(2) films fabricated with a drying step after each layer deposition are flat and thin without porous structures. In situ atomic force microscopy (AFM) measurements confirm that the sodium silicate and TiO(2) nanoparticles are deposited in their aggregated forms. A N(2) drying step can disintegrate the aggregated silicate and TiO(2) nanoparticles to produce thin silicate/TiO(2) films with compact structures. Without the drying steps, the aggregated silicate and TiO(2) nanoparticles are well retained, and their LbL assembly produces highly porous silicate/TiO(2) films of large thickness. The highly porous silicate/TiO(2) films are demonstrated to be useful as reusable film adsorbents for dye removal from wastewater because they can adsorb a large amount of cationic organic dyes and decompose them under UV irradiation. The present study is meaningful for exploring drying/nondrying steps for tailoring structure and functions of LbL assembled films.     

Pore-scale modelling and tomographic visualisation of drying in granular media

Spatio-temporal evolution of liquid phase clusters during drying of a granular medium (realised by random packing of cylindrical particles) has been investigated at the length-scale of individual pores. X-ray microtomography has been used to explicitly resolve the three-dimensional spatial distribution of the solid, liquid, and gas phases within the wet particle assemblies. The propagation of liquid menisci through the granular medium during drying was dynamically followed. The effect of contact angle on the degree of dispersion of the drying front has been studied by observing drying in a layer of untreated (hydrophilic) and silanised particles; the drying front was found to be sharper in the case of the silanised (less hydrophilic) particles. This observation was confirmed by direct numerical simulations of drying in a digitally encoded porous medium identical in structure to the experimental one. The simulations also revealed that the average gas-liquid interfacial area in a given porous microstructure strongly depends on the contact angle.     

Integration of biomass drying with combustion/gasification technologies and minimization of emissions of organic compounds

Moisture content (MC) of green biomass or raw biomass materials (wood, bark, plants, etc.) commonly exceeds 50 mass % (wet basis). The maximum possible MC of biomass fuel for big scale combustion (e.g. fluidized bed combustion with low external heat losses) is approximately 60–65 mass %. Higher biomass MC generally causes operational problems of biomass combustors, lower stability of burning and higher CO and VOC emissions. Gasification of biomass with higher MC produces fuel gas of lower effective heating values and higher tar concentrations. In this review, various technological schemes for wood drying in combination with combustion/gasification with the assessment of factors for possible minimization of emissions of organics from the drying processes are compared. The simple direct flue gas biomass drying technologies lead to exhaust drying gases containing high VOC emissions (terpenes, alcohols, organic acids, etc.). VOC emissions depend on the drying temperature, residence time and final MC of the dried biomass. Indirect biomass drying has an advantage in the possibility of reaching very low emissions of organic compounds from the drying process. Exhaust drying gases can be simply destroyed as a part of the total combustion air (gas) in a combustion chamber or a gasifier. Liquid, condensed effluents have to be treated properly because they have relatively high content of organic compounds, some of them accompanied by odor. Drying of biomass with superheated steam offers more uniform drying of both small and bigger particles and shorter periods of higher temperatures of the dried biomass, particularly if drying to the final MC below 15 mass % is required. In practical modern drying technologies, biomass (mainly wood) is dried in recirculated gas of relatively high humidity (approaching saturation) and the period of constant rate drying is longer. Drying of moist wood material (saw dust, chips, etc.) is required in wood pellet production. Emissions of organics in drying depend on biomass properties, content of resins, storing time and on operational aspects of the drying process: drying temperature, drying medium, final MC, residence time, and particle size distribution of the dried biomass (wood). Integration of biomass drying with combustion/gasification processes includes the choice of the drying medium (flue gas, air, superheated steam). Properties of the drying media and operational parameters are strongly dependent on local conditions, fuel input of the combustion/gasification unit, cleaning of the exhaust drying media (gas, steam, wastewater), and on environmental factors and requirements.     

基于Pd/COF-LZU1非标记型C-反应蛋白免疫传感器的研制

采用溶剂热法, 通过有机单体合成了一种亚胺键连接的共价有机框架材料(COF-LZU1); 在常温常压条件下, 通过后合成的方法将贵金属钯(Ⅱ)引入到COF材料中, 合成了复合材料Pd/COF-LZU1, 该材料具有优良的催化性能. 利用Pd/COF-LZU1多孔复合材料将C-反应蛋白(CRP)抗体(anti-CRP)固定在玻碳电极表面, 构建了一种非标记型CRP免疫传感器. 当抗体与抗原发生免疫反应时, 形成的免疫复合物会阻碍电化学探针[Fe(CN)₆]^4-/3-的电子传递, 降低其响应电流, 从而实现CRP的快速检测. 采用交流阻抗和差示脉冲伏安法(DPV)考察了免疫传感器的电化学特性, 同时考察了测试底液的pH值、 抗原培育时间和抗体固定浓度等实验条件对传感器性能的影响. 在最优的实验条件下, 采用DPV法对CRP进行检测的线性范围为5~180 ng/mL, 检出限为1.66 ng/mL, 线性相关系数为0.992.     

Porous Silica‐Coated Gold Nanorods: A Highly Active Catalyst for the Reduction of 4‐Nitrophenol

The successful coating of thin porous silica layers of various thicknesses [(10±1), (12±1), and (14±1) nm] on cetyl trimethylammonium bromide (CTAB) capped gold nanorods was achieved through a modified Stöber procedure. The resulting material was applied as a novel catalyst for the reduction of 4‐nitrophenol. The catalytic activities of the gold nanorods increased up to eight times after coating with a layer of porous silica and the reaction followed a zero‐order kinetics, having a rate constant as high as 2.92×10^?1 mol L^?1 min^?1. The spectral changes during the reduction reaction of 4‐nitrophenol were observed within a very short span of time and a complete conversion to 4‐aminophenol occured within 5–6 mins, including the induction period of ≈2 mins. The reusability of the catalyst was studied by running the catalytic reaction during five consecutive cycles with good efficiency without destroying the nanostructure. The methodology can be effectively applied to the development of composite catalysts with highly enhanced catalytic activity.     

Micrometrically controlled surface modification of Teflon by redox catalysis: electrochemical coupling between Teflon and a gold band ultramicroelectrode

Carbon-fluorine bonds of Teflon (polytetrafluoroethylene, PTFE) can be reduced electrochemically with the purpose of modifying its adhesive and wetting surface properties by micrometrically controlled surface carbonization of the material. This can be performed adequately by redox catalysis provided that the redox mediator couple has a sufficiently negative reduction potential. The process is investigated kinetically with benzonitrile as the mediator and a gold-band ultramicroelectrode mounted adjacent to a PTFE block, though separated from it by an insulating micrometric mylar gap. For moderate fluxes of reduced mediator, the whole device behaves as a generator-collector double-band assembly with a constant current amplification factor. This is maintained over long periods of time, during which the carbonized PTFE zones extends over distances that are much wider than the slowly expanding cylindrical diffusion layer generated at the gold-microband electrode. This establishes that the overall redox catalysis proceeds through electronic conduction in the n-doped carbonized material. Thus, carbonization progresses at the external edge of the freshly carbonized surface in a diffusion-like fashion (dependence on the square root of time), while the redox-mediator oxidized form is regenerated at the carbonized PTFE edge facing to the gold ultramicroelectrode, so that the overall rate of carbonization is controlled by solution diffusion only. For larger fluxes of mediator, the heterogeneous rate of reduction and doping of PTFE becomes limiting, and the situation is more complex. A conceptually simple model is developed which predicts and explains all the main dynamic features of the system under these circumstances and allows the determination of the heterogeneous rate constant of carbon-fluorine bonds at the interface between the carbonized zone and the fresh PTFE. This model can be further refined to account for the effect of ohmic drop inside the carbonized zone on the heterogeneous reduction rate constants and henceforth gives an extremely satisfactory quantitative agreement with the experimental data.     

Characterization of ultrafiltration membranes by drying

Since the drying rate curves of membranes are comparable to those of porous solid materials, it should be possible to obtain information on membrane structure and the state of water within the membrane from membrane drying experiments and the theory of drying. When membranes are dried on one side either through the active skin or the skin of the porous sublayer, a drying rate curve is obtained which characterizes the membrane. This paper describes how the drying rate curve can give information on the asymmetry of the membranes, on the degree of water uptake after drying, and on the effect of surfactants on rewetting. The drying curve can also be used to examine the effect of membrane manufacture on membrane structure. It has also been shown that partial drying may result in loss of permeability due to loss of the larger pores in the active skin. For the investigations reported in this paper, polyamide and polysulfone ultrafiltration membranes were used.     

Influence of membrane layer properties on the electrophoretic behavior of a soft particle

The influence of the physical properties of the membrane layer of a soft particle, which comprises a rigid core and a porous membrane layer, on its electrophoretic behavior, is investigated. Because that influence was almost always neglected in the previous studies, the corresponding results can be unrealistic. The applicability of the model proposed is verified by the available theoretical and experimental results. The electrophoretic mobility of the particle under various conditions is simulated through varying the dielectric constant, the thickness, and the drag coefficient of the membrane layer, and the bulk ionic concentration. We show that under typical conditions, the deviation in the electrophoretic mobility arising from assuming that the dielectric constant of the membrane layer is the same as that of the bulk liquid phase can be in the order of 50%. In addition, the thicker the membrane layer and/or the higher the bulk ionic concentration, the larger the deviation. If the surface of the core of the particle is charged, as in the case of inorganic particles covered by an artificial membrane layer, the deviation at constant core surface potential is larger than that under other types of charged conditions. However, if the surface of the core is uncharged, as in the case of biocolloids, then that deviation becomes negligible. These findings are of fundamental significance to theoreticians in their analysis on the electrokinetic behaviors of soft particles, and to experimentalists in the interpretation of their data.     

Drying of alkoxide gels—Observation of an alternate phenomenology

The process of drying of a porous material as per the current phenomenological theory can be divided into two stages. At first the body shrinks by an amount equal to the volume of liquid that evaporates, and the liquid-vapor interface remains at the exterior surface of the body. The second stage begins when the body becomes too stiff to shrink and the liquid recedes into the interior, leaving air filled pores near the surface. We shall refer to this phenomenology as the drying front model. In our investigation of drying of alkoxide silica gels of less than 50 Angstroms pore radius, we have observed a different drying pattern, in which even after the gel body stops shrinking, drying continues to occur by evaporation on the exterior surface of the gel body, causing spontaneous nucleation of partially or fully dried opaque clusters, randomly distributed in the interior parts of the gel. These clusters than increase in number and size till they coalesce to form an opaque body. Upon further drying, the gel returns to its transparent form. We postulate that this is possible only if the rate of fluid flow in the pores by diffusion is faster than that by Darcy's flow, as well as the evaporation rate at the surface of the gel body. We shall refer to this as the cluster drying model. We shall present results of pin-hole drying experiments on cylindrical alkoxide gels showing that for identical gels the evaporation rate can be increased to change the phenomenology from cluster drying to one that exhibits both phenomenology simultaneously and finally to that of the drying front phenomenology. We shall also show the effect of gel pore size distribution on the phenomenology of drying under identical drying conditions. Finally, we will present evidence that for successful drying of large cylindrical alkoxide gels, drying conditions favoring cluster drying phenomenology is desirable.     

Source-like solution for radial imbibition into a homogeneous semi-infinite porous medium

We describe the imbibition process from a point source into a homogeneous semi-infinite porous material. When body forces are negligible, the advance of the wetting front is driven by capillary pressure and resisted by viscous forces. With the assumption that the wetting front assumes a hemispherical shape, our analytical results show that the absorbed volume flow rate is approximately constant with respect to time, and that the radius of the wetting evolves in time as r ≈ t(1/3). This cube-root law for the long-time dynamics is confirmed by experiments using a packed cell of glass microspheres with average diameter of 42 μm. This result complements the classical one-dimensional imbibition result where the imbibition length l ≈ t(1/2), and studies in axisymmetric porous cones with small opening angles where l ≈ t(1/4) at long times.     

Gel layer formation and hollow fiber membrane filterability of polysaccharide dispersions

Gel layer formation on the membrane surface during filtration plays a significant role in membrane fouling that, in many instances, controls water production and energy consumption in the treatment of waters and wastewaters. In this study, alginate is selected as a model of the polysaccharides prevalent in wastewaters which, on membrane filtration, may form a gel on the membrane surface which subsequently limits filtrate throughput. We show that over the range of the applied pressures of 11.7–135 kPa considered here, constant pressure ultrafiltration of alginate follows the behavior of cake filtration. The material properties of the alginate are determined by the employment of the previously developed steady-state filtration approach. The consolidation of the gel layer is found to be controlled by the hydraulic flow resistance rather than the rearrangement of particles. Under these conditions, it is valid to apply the derived material properties for the quantification of both constant pressure and constant flux filtration. The gel layer formed from alginate is very compressible and far from uniform over its depth. Within the range of the applied pressures, the gel layer is very porous with a water content of more than 96% but very low Darcy permeability of less than 1 × 10⁻¹⁷ m². During hollow fiber membrane filtration, the local flux is neither uniform nor constant along the fiber length, resulting in non-uniformity of the growth rate, the average porosity and the thickness of the gel layer. The non-uniformity is most apparent at the start of filtration and then gradually diminishes as the gel layer builds up with ongoing filtration.     

Constructing Mie‐Scattering Porous Interface‐Fused Perovskite Films to Synergistically Boost Light Harvesting and Carrier Transport

Light harvesting (LH) and carrier transport abilities of a photoactive layer, which are both crucial for optoelectronic devices such as solar cells and photodetectors (PDs), are typically hard to be synergistically improved. Taking perovskite as an example, a freeze‐drying recrystallization method is used to construct porous films with improvements of both LH and carrier transport ability. During the freeze‐drying casting process, the rapid solvent evaporation produces massive pores, the sizes of which can be adjusted to exploit the Mie scattering for enhancement of the LH ability. Meanwhile, owing to the strong iconicity, the interface between perovskite nanocrystals fused during recrystallization, which favors carrier transport. Subsequently, PDs based on these Mie porous and interface‐fused films show a high on/off ratio of more than 10⁴ and an external quantum efficiency value of 658 % under 9 V bias and 520 nm light irradiation.     

Porous carbon-carbon composite replicated from a natural fibre

Highly porous carbon composites, suitable to be used as electrodes in electrochemical double layer capacitors, could be produced by pyrolysis of resorcinol-formaldehyde resins impregnated onto a natural fibre material (celullosic fabric), without additional template agents or special drying of the polymer gels.     

1.1 μm superficially porous particles for liquid chromatography. Part I: synthesis and particle structure characterization

Superficially porous particles are characterized by a non-porous particle core surrounded by a thin porous layer. Superficially porous particles have been shown to have chromatographic advantages over traditional totally porous particles by reducing the resistance to mass transfer and the eddy diffusion contributions to the theoretical plate height, particularly for biomolecule separations. Currently, 1.7 μm superficially porous particles are commercially available, but a further decrease in the particle diameter and reduction in the porous layer thickness has the potential to further improve the efficiency of the column packing material. In this study, the synthesis of smaller diameter superficially porous particles was investigated. As the particle diameter was decreased, however, synthesis parameters previously reported were rendered unsuitable due to particle agglomeration, non-uniform coating, and porous layer disintegration. Parameters such as colloidal silica size, drying process, and sintering temperature were investigated to improve the structural characteristics of smaller diameter superficially porous particles. Reported is a synthetic route for production of 1.1 μm superficially porous particles having a 0.1 μm porous layer. Based on the revised method, the particles produced have a surface area, pore diameter, and particle size distribution RSD of 52 m²/g, 71 Å, and 2.2%, respectively.     

浓差极化的介电模型——复合膜/溶液体系的数值模拟

提出了具有电导率和介电常数线性分布的介质的介电模型, 并导出了其内部电的和结构性质的参数与宏观测量的电容和电导之间定量关系的理论表达式, 以模拟复合膜中的多孔层部分的介电弛豫行为. 大量的模拟计算描述并解释了多孔层介电谱随介电常数分布、厚度等性质而变化的规律. 进一步对具有层状构造的复合膜以及复合膜和溶液相组成的多层体系的弛豫行为进行了数值模拟, 比较了三个体系(多孔层、复合膜、复合膜/液相层状体系)的介电谱, 结果揭示了介电谱对各层性质的依赖关系. 所提出的电导率和介电常数线性分布的多孔层的介电模型, 也可用于具有其他电导率、介电常数分布规律的体系.