Control of the permeability of a porous media using a thermally sensitive polymer

Experiments explore the reduction in permeability of a porous bead pack when a suspension of thermally responsive polymer is injected and the temperature then increased above the thermal activation temperature. The change in permeability is greater with higher polymer concentration, provided that the ionic concentration of the solution is sufficient for floc formation. The time for activation of the blocking effect is within tens of seconds to minutes of when the polymer solution is heated. This is consistent with the timescale for diffusion‐limited aggregation, although the detailed value depends on the geometry and polymer concentration. Dynamical experiments demonstrate that once the porous media is blocked, adding additional polymer has no effect. The mechanism for permeability reduction may be modeled in the context of a pore‐network model, and we build a simple model to illustrate the permeability reduction as a function of the fraction of pores links which are blocked. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1193–1201, 2014     

Tuning the pore size and surface area of monodisperse Poly(Methyl Acrylate) beads via parallel seeded polymerisation

A library of 36 monodisperse Poly(Methyl Acrylate)(PMA) beads prepared by seeded polymerisation, for potential application in bio-separations and coatings, were synthesized in a high-throughput (HT) manner and analysed with respect to pore size, surface area and morphology. Beads with high porosity were obtained even with a minimum swelling time of 1 h. Both poly(vinyl alcohol) (PVA) and sodium n-dodecyl sulfate (SDS) were used as the surfactants to obtain particles with a high roundness index. The surface areas were essentially controlled by the ratio of the seed particles introduced in the system relative to the monomer, but did little to affect the average pore size. Increasing the swelling time from 1 to 48 h did not make any significant change in the particle morphology. High surface areas (84 m²/g) and pore sizes up to 110 Å could be induced by judicious choice of solvent, while increasing concentrations of so called ‘good solvents’ increased the surface areas.     

Dual role of activated carbon as fuel and template for solution combustion synthesis of porous zinc oxide powders

In this work, nanosized zinc oxide (ZnO) powders were fabricated by urea–nitrate solution combustion synthesis using activated carbon as a structure-directing template and secondary fuel at different fuel–oxidant ratios. The as-synthesized powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption–desorption measurements, UV–Vis diffuse reflectance spectroscopy, and photoluminescence. The effect of fuel amount on photocatalytic activity of ZnO powders was evaluated by the degradation of an azo dye Orange G. It was observed that combustion synthesis with activated carbon as a secondary fuel had a profound effect on reducing crystallite size and enhancement of specific surface area. The crystallite size of the as-synthesized powders varied from 46 to 26 nm. The ZnO powder prepared at a fuel–oxidant ratio of 1.8 possessed the small crystallite size and high specific surface area of 69 m²/g. It correspondingly resulted in the highest dye removal percentage of 99% with a rate constant of 0.027 min⁻¹. The improvement in dye degradation can be due to the synergistic interaction and interplay of enhanced surface area and catalytic ability of the photocatalyst. This study provides a simple single-step synthesis methodology to produce metal oxide nanopowders with tunable surface properties for high potential applications in catalysis, optoelectronics, and gas sensors.     

Influence of the boundary conditions on capillary flow dynamics and liquid distribution in a porous medium

After depositing a wetting liquid onto a porous medium surface, and under the influence of the capillary pressure, the liquid is imbibed into the porous medium creating a wetted imprint. The flow within the porous medium does not cease once all the liquid is imbibed but continues as a secondary capillary flow, where the liquid flows from large pores into small pores along the liquid interface. The flow is solved using the capillary network model, and the influence of the boundary condition on the liquid distribution within the porous medium is investigated. The pores at the porous medium boundaries can be defined as open or closed pores, where an open pore is checked for the potential threshold condition for flow to take place. In contrast, the closed pore is defined as a static entity, in which the potential condition for flow to take place is never satisfied. By defining the pores at distinct porous medium boundaries as open or closed, one is able to obtain a very different liquid distribution within the porous medium. The liquid saturation profiles along the principal flow direction, ranging from constant to steadily decreasing, to the profile with a local maximum, are found numerically. It is shown that these saturation profiles are also related to the geometrical dimension that is perpendicular to the flow principal direction, and changing the boundary type from open to closed allows the liquid distribution within the porous medium to be controlled. In addition to the liquid distribution, the influence of the boundary conditions on capillary pressure and relative permeability is investigated, where both parameters are not influenced by variation of the boundary condition types. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

溶胶凝胶法多孔炭材料的制备及其表征

以十六烷基三甲基溴化胺(CTAB)稳定过的商业硅溶胶为模板硅源、蔗糖为炭前体、运用溶胶凝胶法制备了多孔炭材料。并采用低温N2等温吸脱附、X射线衍射等对材料的结构进行了测试与表征。结果表明:CTAB的加入使所得的多孔炭孔径分布更加集中,由于炭化温度较低,所得的炭材料仍为无定形结构。     

多孔炭材料设计合成及电化学储能应用

多孔炭材料具有导电性好、结构稳定、资源丰富、价格低廉的天然优势,既可直接作为电极材料,构建炭基电化学储能器件,又可与非炭电活性材料复合,起到传输电子、缓冲体积膨胀及调节界面反应的作用,在电化学储能器件中一直发挥着不可或缺的作用。结合本文作者课题组的研究工作,本文总结了多孔炭制备及孔结构和形貌的调控方法,分析了各方法的优缺点;并以超级电容器、锂离子/钠离子电池和锂硫电池为代表,阐述了多孔炭材料在电化学储能领域的作用及应用研究现状,讨论了电化学储能器件对多孔炭材料的结构与性能要求,指出了多孔炭在电化学储能应用中存在的局限性,并对多孔炭在这些储能领域的研究和发展趋势做出展望。     

Dual-template synthesis of hierarchical porous carbon and its application in electrical double-layer capacitors

Hierarchical porous carbons (HPCs) with tailored pore structure were fabricated via direct carbonization of a precursor consisting of agar and acetates in an inert atmosphere. The agar served as the carbon source and curing agent, while potassium acetate and calcium acetate were used to create micropores and mesopores, respectively. The morphology and structural features of the HPCs were characterized, and the electrochemical properties were estimated in a three-electrode system with 6 M KOH as the electrolyte. The resulting HPCs possess a developed pore structure and concentrated pore size distribution (focused at 0.4 and 4 nm), and exhibit typical electrical double-layer capacitive behaviour. Specially, the HCP-2 owns a large specific surface area of 1441.65 m²/g and excellent electrochemical properties, including a favourable specific capacitance (235 F/g at 1 A/g), good rate capability (capacitance retention rate of 88.1% at 20 A/g), and impressive long-term cycling stability (90.6% retention of initial capacitance after 3000 cycles).     

Novel synthesis of thermosensitive porous hydrogels

The simplified method for the synthesis of thermosensitive porous hydrogels by a radical polymerization was presented and their swelling properties were examined experimentally. N,N-Diethylacrylamide (DEAAm) or N-isopropylacrylamide (NIPAm) as primary monomers and N,N′-methylenebisacrylamide (BIS) as a crosslinker were used. They were polymerized in water at various temperatures above the lower critical solution temperature (LCST) of poly-DEAAm (ca. 32°C) or poly-NIPAm (ca. 31°C) by using N,N,N′,N′-,tetramethylethylenediamine (TEMED) and ammonium peroxsodisulfate (APS) as the polymerization accelerator and initiator, respectively. From the observation by a scanning electron microscope, it was found that these gels consisted of aggregated microgel particles, namely, a porous structure. The gels swelled below their LCSTs, and the swelling degree increased with lowering temperature. Furthermore, the gels swelled or shrank very fast in response to the change in temperature, and the shrinking rate was larger than the swelling rate. Such swelling properties and mechanical properties depended on the porous structure of the gels such as the size of the microgels and the pore volume, which largely changed with the synthesis temperature and the component of the primary monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 895–906, 1998     

N掺杂多孔碳材料研究进展

通过掺杂氮原子对多孔碳材料进行功能化,可强化多孔碳材料固有的优异性能并赋予其新功能,从而拓宽其在各领域的应用范围。近年来,研究者相继开发了一系列技术方法,已制备得到多种结构特异、性能优异的氮掺杂多孔碳材料。本文基于氮掺杂多孔碳材料的最新研究进展,详细介绍了利用液相模板法、化学气相沉积法、氨气后处理法、化学活化法和水热法等制备氮掺杂多孔碳材料的方法,评述了各种方法的特点及局限性,并简要介绍了该类材料在电池催化、气体吸附分离、储氢及污染气体脱除等方面的应用,指出了氮掺杂多孔碳材料工业应用的规模化制备发展方向。     

碱式碳酸镁催化酚醛聚合制备多孔炭及其CO2吸附性能

利用碱式碳酸镁的催化功能及易分解特性,实现间苯二酚、甲醛的快速凝胶,炭化得到孔隙发达的整体式多孔炭(MCM-Mg),其轴向抗压强度达9.4 MPa。与普通碳酸盐催化的样品相比,MCM-Mg孔隙更为发达。273 K下该系列样品的静态CO₂吸附量可达3.49~4.50 mmol·g^-1 (0.1 MPa),0.015 MPa最高可达1.87 mmol·g^-1。研究发现,微孔对材料吸附性能起主导作用;MCM-Mg的单位微孔比表面积可吸附7.15 μmol CO₂,超过了大部分活化法制备的炭材料。多组分动态穿透实验表明,该系列材料可实现CO₂/N₂的完全分离;材料具有良好的耐水汽性能和循环吸附-脱附性能,室温下经惰性气体吹扫即可实现再生。     

Grafting and properties of a porous poly(methyl methacrylate) film on a silicon surface by a one‐step dipping method

In this study, we prepared a porous poly(methyl methacrylate) (PMMA) film on an Si surface with a novel dipping method. We conducted the process by directly dipping the Si substrate into acidic aqueous media in a simple flask at 10 °C. First, 4‐nitrobenzene diazonium tetrafluoroborate (NBD) was spontaneously reduced at the Si surface. Then, the aryl radicals during the reduction of NBD were directly grafted onto the Si surface. Meanwhile, the aryl radicals initiated the polymerization of methyl methacrylate (MMA) monomers, and the radical‐terminated PMMA chains formed in the solution were grafted onto the Si surface. Because water was a poor solvent for MMA, the grafted PMMA chains easily aggregated together, and this resulted in a porous polymer film. The porosity of the film depended on the grafting time and the MMA concentration. Furthermore, the permittivity of the porous PMMA film was relatively low, and its dielectric dissipation factor was extremely small. Therefore, its excellent dielectric properties should allow the porous film to have many applications in industry. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44930.     

多孔碳负载五氧化二铌及其在超级电容器中的应用

以间苯二酚、甲醛和草酸铌为原料,通过原位聚合和高温煅烧,制备出多孔碳负载的五氧化二铌（Nb₂O₅）材料。X射线粉末衍射和扫描电镜分析表明,负载在多孔碳表面上的五氧化二铌具有三维纳米凸起结构,属于正交晶型。循环伏安测试表明该复合材料的比电容达到290 F·g^-1,并具有良好的大电流放电能力,5 A·g^-1的放电电流下,容量可以达到108 F·g^-1。0.5 A·g^-1的首次放电容量为355 F·g^-1 （1.0~3.0 V vs. Li⁺/Li）,100次循环后容量保持率为82%。通过对交流阻抗图谱和等效电路的模拟分析,对其电化学赝电容特性进行了讨论。该复合材料降低了电解液中离子在充放电过程中的迁移路径和扩散阻力,实现Nb₂O₅活性材料的多维度接触,提高了Nb₂O₅的导电性,改善了其超级电容特性。     

岩沥青基多孔碳的制备及其吸附性能研究

采用溶剂萃取法净化天然岩沥青矿,得到岩沥青样品。研究溶剂对天然岩沥青萃取率的影响,当石油醚与二甲苯的质量比为1∶9时,其萃取率高达82.15%。以净化后的岩沥青为原料制备多孔碳,采用SEM、TEM和BET等方法对材料进行表征,探究助剂脒基硫脲(AU)和硫酸铵(AS)对多孔碳(PC)形貌和结构的影响。BET分析结果表明:AU/PC和AS/PC的比表面积分别为56 m^(2)/g和466 m^(2)/g,总孔容分别为0.113 cm^(3)/g和0.365 cm^(3)/g,AS/PC的孔径主要分布在1.7~3.0 nm,具有丰富的孔隙结构。同时探究了岩沥青基多孔碳材料对水溶液中Cd(Ⅱ)的吸附性能。     

多孔氧化铝模板法制备取向碳纳米管阵列的研究进展

利用化学气相沉积技术在多孔氧化铝模板上可以制备取向碳纳米管阵列。通过调节阳极氧化参数可以改变模板的孔结构,进而可控制碳纳米管在孔道中生长的形貌。用这种方法制备的碳纳米管的直径、长度和密度可以选择性控制,这将有利于研究碳纳米管的性质和它在电化学及其他领域的应用。介绍了多孔氧化铝模板的形成原理以及碳纳米管在多孔氧化铝模板上的生长机理,讨论了阳极氧化条件、催化剂和气相沉积温度对碳纳米管特性的影响,并指出了这种技术中一些需深入研究的问题。     

Green and continuous microflow synthesis of fluorescent carbon quantum dots for bio-imaging application

In this work, a simple, continuous and completely green method based on microflow technique is demonstrated for the synthesis of carbon quantum dots (CQDs) from diverse bio-based precursors. CQDs prepared from milk is illustrated as a case study to show the process feasibility. Crystalline fluorescent CQDs of 12.53% quantum yield and good stability are synthesized by the approach, even at 120°C. Systematic experiments further suggest their optical properties, bandgap energy, and fluorescence lifetime are closely related to the synthesis temperature. The maximum production rate of the CQDs was 51.1 mg/h at 180°C. Cytotoxicity and cellular imaging tests against 3T3 cells reveal the CQDs possess high biocompatibility, and can penetrate cell membranes and display bright fluorescence. The process versatility is investigated by expanding the precursor to watermelon juice, orange juice, and soy milk, indicating successful synthesis of small-sized CQDs of low cytotoxicity and strong photoluminescence by the technique.     

Facile synthesis of bimodal porous silica and multimodal porous carbon as an anode catalyst support in proton exchange membrane fuel cell

A simple and easy sol-gel approach has been developed to directly synthesize in situ three-dimensionally interconnected uniform ordered bimodal porous silica (BPS) incorporating both the macroporosity and mesoporosity in the lattice without extra synthesis process performed in previous work. Multimodal porous carbon (MPC) was fabricated through the inverse replication of the BPS. The unique structural characteristics such as well-developed 3-D interconnected ordered macropore framework with open mesopores embedded in the macropore walls, large surface area (1120 m² g⁻¹) and mesopore volume (1.95 cm³ g⁻¹) make MPC very attractive as an anode catalyst support in polymer exchange membrane fuel cell. The MPC-supported Pt-Ru alloy catalyst has demonstrated much higher power density toward hydrogen oxidation than the commercial carbon black Vulcan XC-72-supported ones.     

Fate of a sessile droplet absorbed into a porous surface experiencing chemical degradation

A general‐purpose multiphase and multicomponent computer model was developed for simulation of the spread, evaporation, and chemical reaction of sessile droplet(s) in porous substrates. In the model, chemical reactions were allowed in or between any of the liquid, gas, or solid phases present. The species mass and momentum conservation equations were solved on a finite difference mesh representing the domain. These equations were marched in time using the Runge–Kutta fourth‐order method. The model's function was studied via simulation of experiments, both those performed by the authors and found in the literature. These simulations demonstrated a quantitative match to the time history of product evolution and a similar spread of liquid reactants. The model may be particularly beneficial for predicting the extent of contamination and the possible threat outcomes of those chemical agents that are harmful when introduced into the environment. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2557–2565, 2014     

溶胶-凝胶法碳源对多孔炭材料孔隙结构的影响

以正硅酸乙酯(TEOS)为模板硅源,β-环状糊精和可溶性淀粉分别为碳前驱体,运用溶胶-凝胶法制备了多孔炭材料。利用低温N2等温吸脱附、X射线衍射、高倍扫描电子显微镜等对所得炭材料的结构进行了测试与表征,结果表明,β-环糊精为碳源的样品主要孔径分布在2~3 nm;以可溶性淀粉为碳源的样品孔径呈双峰分布,即孔径集中在3.7 nm和5~20 nm,但由于炭化温度较低,所得的炭材料仍为无定形结构。     

多孔有机聚合物催化二氧化碳合成环状碳酸酯研究进展

二氧化碳（CO₂）捕集、利用和储存（CCUS）在全球能源结构转型中是一种极具潜力的策略,能够实现能源供给、基础原料产出以及限制气候变化。多孔有机聚合物（POPs）具有高CO₂吸附容量和吸附选择性、突出的结构特性以及优异的化学可调控性,其作为极具潜力的材料广泛应用于催化CO₂参与的有机反应中。其中,CO₂与环氧化物环加成生成环状碳酸酯的反应具有100%的原子经济性,且其产物也极具工业价值。本文基于CO₂环加成反应催化机制,从催化剂的合成方法、结构性质与组成特性角度出发,综述了POPs在CO₂/环氧化物环加成反应的研究进展,包括金属配合物类、氢键供体类、离子液体类、金属配合物/离子液体和氢键供体/离子液体等有机多孔聚合物体系。通过阐述POPs在催化CO₂制备高附加值环状碳酸酯反应中的研究现状和发展趋势,为POPs的开发与应用以及CO₂综合利用的工业化探索提供具有建设性的指导意见。     

Flow of solutions of hydroxypropyl guar-poly(ethylene oxide) mixtures through a porous medium

Summary In flow through porous media, solutions of poly(ethylene oxide) (PEO) exhibit extension thickening, whereas hydroxypropyl guar (HPG) solutions are shear-thinning at high concentrations. The results show that the extension-thickening exhibited by PEO solutions becomes less critical with increasing flow rate as the concentration of HPG in the solution is increased. At high concentrations of HPG, the presence of PEO inhibits the shear-thinning behaviour, without increasing the apparent viscosity of the solution. The presence of HPG reduces the rate and extent of degradation of PEO in the flowing solution.