工艺参数对天然沸石模板多孔炭结构的影响

以内蒙古赤峰市的天然沸石矿为模板，以蔗糖为炭的前驱体，制备了具有较窄中孔孔径分布的模板多孔炭。利用SEM、XRD及N2吸附等方法对模板炭进行了表征。采用BJH法分析了模板炭的孔径分布特征。研究了制备工艺中催化剂H2SO4的用量和炭化温度对所得模板多孔炭结构的影响。结果表明，硫酸用置和炭化温度对模板多孔炭的表面形貌、微晶结构和孔结构都有一定的影响。催化剂H2SO4用置过多时模板炭表面结构粗糙、致密，杂质较多，比表面积和总孔容较小；炭化温度越高，模板炭的结构收缩越严重，总孔容和中孔孔容越大，中孔率越高。     

用于超级电容器的生物形态多孔炭的制备及表征

以天然木质材料为原料,以ZnCl2为活化剂,采用一步化学活化法制备了保留木材天然结构的生物形态多孔炭。研究了活化工艺参数对多孔炭的孔结构和表面形貌的影响,并初步探讨了活化机理。结果表明:活化剂ZnCl2对于生物形态多孔炭具有很好的活化作用,通过改变ZnCl2/多孔炭的浸渍比、活化温度,可以调控多孔炭的孔结构和表面形貌。活化温度450℃,浸渍比为7时,多孔炭的BET比表面积为771.6m2/g;浸渍比为5,活化温度900℃,多孔炭的BET比表面积为951.34m2/g。ZnCl2具有催化脱羟基和脱水的作用,并促进芳烃缩合反应,对多孔炭表面产生造孔和扩孔作用,随着浸渍比的提高和活化温度的升高,扩孔作用明显。     

烧结工艺对炭球孔结构的影响

多孔炭球是应用在有害气体吸附、超级电容器及血液渗透等领域中的关键材料,其孔结构及性能由原料种类及制备工艺等共同决定。以磺化苯乙烯-二乙烯基苯阳离子交换树脂为原料通过化学气相沉积法(CVD)制备多孔炭球,通过扫描电镜及比表面积分析研究了不同热处理条件对所制炭球孔结构的影响。实验表明:烧结工艺对多孔炭球的形貌及结构有很大影响。具体来说,炭化温度的提高整体上有利于孔结构的形成;升温速率提高有利于介孔、大孔结构的形成;活化有利于形成微孔结构。以上研究对炭球孔结构的可控制备有一定意义。     

炭化温度对多孔炭涂覆蜂窝陶瓷整体式催化剂的影响

以糠醇树脂为炭前驱体,在不同炭化温度下制备出系列涂层型多孔炭涂覆蜂窝陶瓷整体式催化剂。N2-物理吸附和程序升温脱附(TPD)的表征结果表明,炭化温度对多孔炭涂层的物理-化学性质均有较大影响,随着炭化温度升高,多孔炭涂层孔结构的形成趋于完全,同时涂层表面酸性含氧基团的种类和数量逐渐减少,800℃时多孔炭涂层孔结构完全形成,且表面酸性含氧基团也基本消失。1,1,2,2-四氯乙烷气相催化脱HCl合成1,1,2-三氯乙烯反应评价结果表明,孔结构和表面酸性含氧基团是影响多孔炭催化性能的关键因素,800℃炭化的多孔炭涂覆蜂窝陶瓷整体式催化剂的催化活性、选择性和稳定性最佳。     

SiC多孔陶瓷预成形坯的制备

本文采用真空烧结方法制备SiC多孔陶瓷预成形坯,研究了不同助烧结剂Al2O3-Y2O3、Si、Co和高岭土以及造孔剂羧甲基纤维素(CMC)含量对SiC多孔陶瓷预成形坯气孔率和形貌的影响。结果表明,多元助烧剂Al2O3-Y2O3有利于降低烧结温度和形成液相烧结,并有利于提高SiC多孔陶瓷的孔结构稳定性;羧甲基纤维素含量对烧结预成形坯气孔率和体积密度的影响较大,随着造孔剂CMC含量的增加,SiC多孔陶瓷的气孔率也相应地增加,其体积密度相应减少。     

玉米芯制备多孔炭及其孔结构的表征

以小于20目的玉米芯为原料，以水蒸气为活化剂，在N2保护下，采用物理活化法制备多孔炭，考察了炭化温度、炭化时间、操作方式以及活化时间等操作条件对多孔炭收率、比表面积和孔结构参数等的影响。同时采用N2吸附法，对多孔炭的比表面积及孔结构进行了表征。实验结果表明：经过800□炭化30min，并采用恒温时加料，恒温时取出的操作方式，是制备较高比表面积多孔炭的最佳炭化条件：在同一活化温度下，为得到收率较高的产品，不易延长其活化时间；经过对原料进行酸处理和热压成型，可以提高多孔炭的收率，增加多孔炭的比表面积和总孔容。     

具有发达中孔的多孔炭材料的研究进展

本文综述了国内外在调控多孔炭材料孔径分布，特别是提高其中孔率方面的研究进展，着重介绍了催化活化、界面活化、混合聚合物炭化、有机凝胶炭化、铸型炭化等孔径调控技术及其孔结构形成机理。为控制多孔炭材料的孔径大小和分布，提出其中孔容积（率）和吸附性能提供了理论和实验依据。     

具有多级孔道结构的高比表面多孔炭活化策略及VOCs吸附性能

以废弃榛壳为前体,采用不同活化策略制备多孔炭,探究活化策略和活化温度对多孔炭挥发性有机化合物（VOCs）吸附性能的影响,以及多孔炭的结构、表面性质与VOCs吸附性能的构效关系。结果表明,H₃PO₄法制备的多孔炭介孔体积大,且炭结构缺陷较少,吸附位点较少; KOH法获得的微孔体积较大,孔径集中在0.5~0.7nm的微孔,不利于VOCs分子吸附位点的有效利用。H₃PO₄-KOH分步法在850℃下制备具有高比表面积,孔径集中在0.5~1nm的宽微介孔分布,且炭结构高度无序并含有丰富缺陷位的多孔炭,为VOCs吸附提供了充足的吸附位点并提高了吸附位点了利用率,相比于H₃PO₄与KOH活化法制备的多孔炭的VOCs饱和吸附量显著提升,特别是对于弱极性VOCs。另外,H₃PO₄-KOH分步法制备的多孔炭表面官能团含量较低,极性较低,对非极性VOCs的吸附量远大于极性VOCs。因此,H₃PO₄-KOH分步活化策略是制备具有高比表面积、高VOCs吸附性能多孔炭的最优策略与方案。     

酚醛树脂基多孔炭材料制备的研究

以酚醛树脂为炭前驱体、聚乙烯醇缩丁醛(PVB)为造孔剂,采用聚合物共混炭化法制备了多孔炭材料,考察了造孔剂PVB的含量、炭化温度和炭化时间对多孔炭材料比表面积和孔结构的影响.结果表明,在造孔剂PVB的含量为40%、炭化温度为700℃、炭化时间为1.0 h的条件下,可制得BET比表面积为540.4 m2·g-1、孔容为0.37 cm3·g-1、平均孔径为7.298 nm的多孔炭.     

基于偏氯乙烯嵌段共聚物的多级多孔炭的制备

采用可逆加成-断裂链转移（RAFT）活性自由基聚合制备了聚苯乙烯-b-聚偏氯乙烯-b-聚苯乙烯嵌段共聚物（PS-b-PVDC-b-PS）,以此嵌段共聚物为碳前驱体,直接碳化制备微孔-中孔复合多级多孔炭。采用凝胶渗透色谱仪和核磁共振仪表征了嵌段共聚物结构,表明通过RAFT聚合可制得分子量较高（M_n^GPC >6000 g·mol^-1）和分子量分布较窄（PDI<1.5）的PS-b-PVDC-b-PS。采用热重分析表征嵌段共聚物热解特性,采用扫描电镜、N₂吸脱附表征多孔炭形貌和孔隙结构。结果表明嵌段共聚物同时具有PVDC和PS链段的热失重峰,PS链段可完全热解而具有形成中孔的模板作用,PVDC链段热降解形成含微孔的炭骨架,最终形成兼有微孔和中孔的多级多孔炭;随着PS嵌段含量的增加,嵌段共聚物的成炭率逐渐降低,孔隙尺寸逐渐增大;当PS/PVDC聚合度比为4.3时,多孔炭的比表面积、中孔率和平均孔径达到最大,分别为839 m²·g^-1、54%和2.02 nm。     

Pore structure control of mesoporous carbon monoliths derived from mixtures of phenolic resin and ethylene glycol

Mesoporous carbon monoliths derived from phenolic resin mixtures have been prepared in the process based on polymerization-induced phase separation. The effect of the composition of resin mixtures and the resin curing temperature on the pore structure of carbon monoliths has been systematically investigated, with emphasis on controlling the apparent porosity and pore size distribution. Fractal dimensions have been introduced to evaluate the morphologies of the carbon monoliths. The results showed that mesoporous carbon monoliths with narrow pore size distribution were obtained. The pore structure of carbon monoliths could be controlled by changing the resin curing temperature and the content of ethylene glycol, curing catalyst and water in the resin mixtures. The apparent porosity of carbon monoliths varied from 54.27% to 26.83%. Carbon monoliths had narrower pore size distribution when more ethylene glycol and higher resin curing temperature were employed. The pore structure of carbon monoliths would be changed radically when the initial resin samples were prepared with excess water (9.8 wt%), i.e. porous carbon foams with sponge structure were obtained. Carbon monoliths inherit their porosity from precursing cured resins where it was formed as a result of phase separation of resin-rich and glycol-rich phases. Volume contraction had certain effect on the pore structure of carbon monoliths.     

Development of porous polymer monolith by photoinitiated polymerization

Porous polymer monoliths have been successfully prepared by photoinitiated polymerization of butyl methacrylate (BMA) and ethylene glycol dimethacrylate (EDMA) monomers in porogenic solvent of methanol. Mercury intrusion porosimetry and scanning electron microscope are used to characterize the porous properties; nevertheless, the pore size obtained from both techniques is not comparable. The porous structure of the porous polymers is controlled by the phase separation during the polymerization and crosslinking. By varying the composition of the starting solution such as initiator fraction, BMA/EDMA ratio, porogen fraction, and UV intensity, porous polymers with median pore size from about 140 nm to 3 μm can be obtained, and the pore size distribution for majority of the porous polymers is also narrow. The results present a very positive prospect to microfluidic applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

载体孔结构对银基催化剂性能影响

乙烯氧化制环氧乙烷银催化剂所用载体为大孔惰性α-Al2 O3.载体孔道结构对金属银的分布有调控作用,通过选择适宜的孔道结构,采用银胺溶液浸渍,热分解可以获得特定尺寸分布的负载银催化剂.以不同粒度和晶相的氧化铝复配,添加不同的扩孔剂,制备了孔结构不同的三种载体负载银制得银催化剂.对银催化剂进行TGA和SEM分析,并考察其...     

Controlling porous properties of polymer monoliths synthesized by photoinitiated polymerization

Porous monoliths have been successfully prepared by photoinitiated polymerization of hydroxyethyl methacrylate and ethylene glycol dimethacrylate monomers in a porogenic solvent. By varying the composition of the starting solutions such as initiator fraction, monomer ratio and pore generator (porogen) fraction and type, as well as UV intensity, monoliths have been obtained with narrow pore size distribution and median pore size from about a few nanometres to a few micrometres. © 2012 Society of Chemical Industry     

PolyHIPEs from Methyl methacrylate: Hierarchically structured microcellular polymers with exceptional mechanical properties

Highly porous monoliths with excellent mechanical properties and porosity of up to 90% were prepared by the polymerisation of high internal phase emulsions (HIPE) containing methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA). Materials with open cellular morphology and cavity diameters between 0.6 and 4.5 μm are obtained using a homogenizer and between 0.8 and 25 μm using a standard overhead stirrer. Samples with 80% pore volume have E-moduli up to 180 MPa, while 75% porous samples exhibit E-moduli up to 211 MPa. A dependence of mechanical properties on cavity size distribution is identified, where a more hierarchically developed porous structure results in significantly better mechanical properties.     

Preparation of porous carbon derived from mixtures of furfuryl resin and glycol with controlled pore size distribution

This paper describes the preparation and properties of porous carbon by a technique which consists of mixing a carbon precursor (furfuryl resin and furfural alcohol), a pore-forming agent and a solvent (glycol), polymerizing the resin mixture, and pyrolyzing the hybrid of resin and glycol. The properties of porous carbons have been systematically investigated as a function of composition and heat treatment, with emphasis on understanding and controlling their morphology and pore size distribution. The results seem to indicate that by varying the ratios of the constituents in the polymer system, porous carbons with a wide variation in pore size distribution and morphology can be obtained. Three types of morphologies were observed: interconnected carbon with secondary spherical pores, discrete carbon particulates, and a crosslinked carbon network. Porous carbons with a very narrow pore size distribution have been obtained and the average pore size was controlled between 5 and 0.008 μm. The microstructure of porous carbon formed as a result of phase separation of resin-rich phase and glycol-rich phase, rather than a result of the pyrolysis process. Heat treatment had little effect on the properties of the porous carbons.     

Influence of catalyst pore network structure on the hysteresis of multiphase reactions

The effects of the catalyst pore network structure on multiphase reactions in catalyst pellets are investigated by using the experimentally validated pore network model proposed in our recent work (AIChE J, 62 , 451, 2016). The simulations display hysteresis loops of the effectiveness factor. The hysteresis loop area becomes significantly larger, when having small volume‐averaged pore radius, wide pore‐size distribution, and low pore connectivity; however, the loop area is insensitive to pellet size, even though it affects the value of the effectiveness factor. The hysteresis loop area is also strongly affected by the spatial distribution of the pore size, in particular for a bimodal pore‐size distribution. The pore network structure directly influences mass transfer, capillary condensation, and pore blocking, and subsequently passes these influences on to the hysteresis loop of the effectiveness factor. Recognizing these effects is essential when designing porous catalysts for multiphase reaction processes. © 2016 American Institute of Chemical Engineers AIChE J, 63: 78–86, 2017     

Probing pore blocking effects on multiphase reactions within porous catalyst particles using a discrete model

A discrete model coupling mass transfer, reaction, and phase change in porous catalyst particles is proposed to probe pore blocking effects on multiphase reactions. This discrete model is validated by comparing the results with experiments and those obtained using a continuum model, for the hydrogenation of benzene to cyclohexane in Pd/γ‐alumina catalyst particles. The results show that pore blocking has a significant effect on the effectiveness factor and can contribute to up to 50% of the hysteresis loop area for multiphase reactions in porous catalysts, indicating that pore blocking must be accounted for. Moreover, the pore blocking effects are significantly enhanced when the pore network is poorly connected and the pore‐size distribution is wide, while the pore blocking effects are insensitive to the volume‐averaged pore size. Multiphase catalyst material characterization and design should account for this effect. © 2015 American Institute of Chemical Engineers AIChE J, 62: 451–460, 2016