Asymptotic infiltration into a soil which contains cracks or holes but whose surface is otherwise impermeable

An asymptotic, one-dimensional Green-Ampt model is derived for infiltration into a soil whose surface is impermeable except for regularly spaced vertical cracks, and infiltration into a cylindrical soil column whose top surface is also impermeable except for a central hole. The model is valid at times when the wetting front has become horizontal and corresponds to one-dimensional infiltration initiated from a plane lying above or below the soil surface, depending on the crack spacing/depth ratio (or column radius/hole depth ratio). When applicable, asymptotic Green-Ampt solutions are shown to agree well, in selected cases, with corresponding finite difference solutions of the saturated-unsaturated flow equations.     

Preparation of Silicalite-1 Within Macroporous Silica Glass

Microcrystalline silicalite-1 was formed on the inner surface of macroporus silica glasses prepared by the sol-gel process. By heating a homogeneous precursor solution at 100°C under a hydrothermal condition, 2–5 m of plate-like particles of silicalite-1 were deposited. With an increase of mixing time of the precursor solution, the number of silicalite-1 particles increased, accompanied by the relative decrease of the particle size. Depending on the temperature and the duration of the heat-treatment of the macroporous silica, the amount of deposited silicalite-1 varied. Below 1000°C, the amount increased with the heat-treatment temperature, as a result of the competition between the precipitation of silicalite-1 and the dissolution of silica from the macroporous silica glass under a strongly basic condition. On the other hand, above 1000°C the amount of deposited silicalite-1 decreased in accordance with the decrease of the macropore diameter by the heat-treatment, because of the limited transport of the dissolved silicate species through the smaller macropores.     

Synthesis of Hierarchical Macro‐/Mesoporous Solid‐Solution Photocatalysts by a Polymerization–Carbonization–Oxidation Route: The Case of Ce0.49Zr0.37Bi0.14O1.93

A hierarchical macro‐/mesoporous Ce_0.49Zr_0.37Bi_0.14O_1.93 solid‐solution network has been synthesized on a large scale by means of a simple and general polymerization–carbonization–oxidation synthetic route. The as‐prepared product has been characterized by SEM, XRD, TEM, BET surface area measurement, UV/Vis diffuse‐reflectance spectroscopy, energy‐dispersive X‐ray spectroscopy (EDS), and photoelectrochemistry measurements. The photocatalytic activity of the product has been demonstrated through the photocatalytic degradation of methyl orange. Structural characterization has indicated that the hierarchical macro‐/mesoporous solid‐solution network not only contains numerous macropores, but also possesses an interior mesoporous structure. The mesopore size and BET surface area of the network have been measured as 2–25 nm and 140.5 m² g^?1, respectively. The hierarchical macro‐/mesoporous solid‐solution network with open and accessible pores was found to be well‐preserved after calcination at 800 °C, indicating especially high thermal stability. Due to its high specific surface area, the synergistic effect of the coupling of macropores and mesopores, and its high crystallinity, the Ce_0.49Zr_0.37Bi_0.14O_1.93 solid‐solution material shows a strong structure‐induced enhancement of visible‐light harvest and exhibits significantly improved visible‐light photocatalytic activity in the photodegradation of methyl orange compared with those of its other forms, such as mesoporous hollow spheres and bulk particles.     

“蒸汽相转化”法制备纳米晶组成的块状方钠石多级孔沸石催化材料

将实验室合成的聚苯乙烯乳胶微球（PS）加入制备方钠石（SOD）沸石的前驱体凝胶中,在45℃条件下制得干凝胶,随后采用“蒸汽相转化”法制备了大块状SOD沸石材料。对影响多级SOD沸石形成因素进行了详细讨论。采用X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、N₂吸附-脱附和压汞技术等表征手段对制备的材料进行了详细表征。结果表明通过“蒸汽相转化”法制备的大块状SOD沸石由球状多晶聚集体构成,这些球状多晶聚集体又是由粒径为50~100 nm的初级纳米晶粒组成,在初级纳米晶粒上和纳米晶粒之间形成了2~50 nm介孔结构以及由脱除PS微球形成的50~300 nm的大孔结构。     

Ordered macroporous quercetin molecularly imprinted polymers: Preparation,characterization, and separation performance

Ordered macroporous molecularly imprinted polymers were prepared by a combination of the colloidal crystal templating method and the molecular imprinting technique by using SiO₂ colloidal crystal as the macroporogen, quercetin as the imprinting template, acrylamide as the functional monomer, ethylene glycol dimethacrylate as the cross‐linker and tetrahydrofuran as the solvent. Scanning electron microscopy and Brunauer–Emmett–Teller measurements show that the ordered macroporous molecularly imprinted polymers have a more regular macroporous structure, a narrower pore distribution and a greater porosity compared with the traditional bulk molecularly imprinted polymers. The kinetic and isothermal adsorption behaviors of the polymers were investigated. The results indicate that the ordered macroporous molecularly imprinted polymers have a faster intraparticle mass transfer process and a higher adsorption capacity than the traditional bulk molecularly imprinted polymers. The ordered macroporous molecularly imprinted polymers were further employed as a sorbent for a solid‐phase extraction. The results show that the ordered macroporous molecularly imprinted polymers can effectively separate quercetin from the Gingko hydrolysate.     

“蒸汽相转化”法制备纳米晶组成的块状方钠石多级孔沸石催化材料

将实验室合成的聚苯乙烯乳胶微球(PS)加入制备方钠石(SOD)沸石的前驱体凝胶中,在45℃条件下制得干凝胶,随后采用"蒸汽相转化"法制备了大块状SOD沸石材料。对影响多级SOD沸石形成因素进行了详细讨论。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N_2吸附-脱附和压汞技术等表征手段对制备的材料进行了详细表征。结果表明通过"蒸汽相转化"法制备的大块状SOD沸石由球状多晶聚集体构成,这些球状多晶聚集体又是由粒径为50~100 nm的初级纳米晶粒组成,在初级纳米晶粒上和纳米晶粒之间形成了2~50 nm介孔结构以及由脱除PS微球形成的50~300 nm的大孔结构。     

胶晶模板法制备3DOM尖晶石型LiMn2O4及表征

通过乳液聚合获得粒径为280 nm左右的聚甲基丙烯酸甲酯(PMMA)微球, 从其母液中离心沉降制得胶晶模板. 将LiNO3, Mn(Ac)2·4H2O和柠檬酸按摩尔比1∶2∶2配成前驱物的醇水混合溶液, 填充于PMMA胶晶模板间隙中, 经干燥和焙烧氧化成孔制得了三维有序大孔(3DOM)锂锰氧化物. 实验结果表明, 当n(Li)/n(Mn)=0.6, 前驱液浓度在0.6~1.0 mol/L之间和升温速率为2 ℃/min时, 分别在300与600 ℃下两段恒温焙烧2~3 h有利于目标产物的形成. SEM测试结果表明, PMMA胶晶模板和3DOM锂锰氧化物均为面心立方紧密堆积, 排列规则有序, 大孔直径在200~240 nm之间, 孔壁厚度在30~45 nm之间. 产物经XRD晶相测定和EDTA, KMnO4滴定分析确证为正尖晶石型LiMn2O4.     

新型孔结构渣油催化裂化催化剂

高温短接触FCC工艺和原料的重质化要求FCC催化剂具有大孔，以增加大分子烃在催化剂中的扩散速度，提高催化剂的反应性能。在不改变催化剂组成的前提下，采用聚苯乙烯微球为模板剂在催化剂基质中引入适量的、尺寸可控的大孔；通过SEM、N2吸附等对催化剂的形貌和孔结构进行了表征；以大庆常压渣油为原料，测定了催化剂的反应性能。实验表明，大孔催化剂中孔体积和比表面积随模板剂用量的增加而增加；在模板剂用量相同时，模板剂粒径越小孔体积和比表面积增加越多。模板剂的引入不仅增加了催化剂中的大孔孔体积，使得催化剂中微孔部分的体积和比表面积也有了一定增加。模板颗粒法合成的催化剂，扩散阻力小，重油转化率高，轻油收率高。     

Hierarchically Porous Carbons Derived from Metal–Organic Framework/Chitosan Composites for High‐Performance Supercapacitors

Hierarchically porous carbon materials with high surface areas are promising candidates for energy storage and conversion. Herein, the facile synthesis of hierarchically porous carbons through the calcination of metal–organic framework (MOF)/chitosan composites is reported. The effects of the chitosan (CS) additive on the pore structure of the resultant carbons are discussed. The corresponding MOF/chitosan precursors could be readily converted into hierarchically porous carbons (NPC‐V, V=1, 2, 4, and 6) with much higher ratios of meso‐/macropore volume to micropore volume (V_meso‐macro/V_micro). The derived carbon NPC‐2 with the high ratio of V_meso‐macro/V_micro=1.47 demonstrates a high specific surface area of 2375 m² g^?1, and a high pore volume of 2.49 cm³ g^?1, as well as a high graphitization degree, in comparison to its counterpart (NPC) without chitosan addition. These excellent features are favorable for rapid ion diffusion/transport, endowing NPC‐2 with enhanced electrochemical behavior as supercapacitor electrodes in a symmetric electrode system, corresponding to a high specific capacitance of 199.9 F g^?1 in the aqueous electrolyte and good rate capability. Good cycling stability is also observed after 10 000 cycles.     

Macroporous Activated Carbon Fibers from Rayon Precursors Impregnated with Phosphoric Acid

Novel activated carbon fibers (ACFs) from rayon precursors impregnated with phosphoric acid (H₃PO₄), containing abundant macropores (pore size>50 nm), were successfully obtained. The physical properties of these ACFs were examined. The BET surface was obtained; SEM observations showed that the concentration of H₃PO₄ impregnation strongly influenced the surface morphology and the porous texture of the resulting ACFs. The shape of the pores was nearly round and we could estimate the pore size was distributed between 20 and 150 nm. Infrared spectroscopy (IR) was applied to investigate the pyrolysis process of the rayon precursors with H₃PO_4. In addition, P‐containing substances, which should perhaps be acid phosphates or polyphosphates, can be observed on the surface of the resulting ACFs from SEM photos. Impregnation made the dehydration become more predominant during the pyrolysis process.