连续流微反应器中微纤结构化的Nafion/SiO2固体酸催化苯硝化反应

采用溶胶-凝胶组装方法制备了Nafion/SiO2胶体, 并涂附于烧结的316L不锈钢(SS-316L)金属微纤网络, 形成了空隙率为60%-75%(φ, 体积分数)的整体式微纤结构化的Nafion/SiO2固体酸催化剂. 使用傅里叶变换红外光谱(FT-IR), 热重分析(TGA), 扫描电子显微镜(SEM)及NH3吸附法对微纤结构化的Nafion/SiO2催化剂进行了表征. 结果显示, 溶胶-凝胶组装方法可以明显促进Nafion的分散, 导致酸性中心的暴露量显著增加; 结构化的Nafion/SiO2催化剂以200-400 nm颗粒堆积而成的多孔涂层形式存在. 在一种集换热、混合、催化(反应)功能于一体的微反应器中, 考察了整体式微纤结构化的Nafion/SiO2固体酸催化剂催化苯硝化的反应性能. Nafion在SiO2中的组装量为20%(w, 质量分数), 金属微纤网络上Nafion/SiO2担载量为36.3%(w)的优化催化剂上, 75 ℃时苯转化率为44.7%, 硝基苯选择性可达99.9%. 相近转化率下, Nafion/SiO2固体酸单位酸中心的催化效能约为硫酸的600倍.     

偶联剂改性对γ-Al2O3催化氧化偏三甲苯性能的影响

研究了偶联剂改性的廉价填料级γ-Al_2O_3直接催化偏三甲苯(TMB)氧化为2,3,5-三甲基苯醌(TMBQ)性能的影响。结果表明,γ-(2,3-环氧丙基)丙基三甲氧基硅烷(KH560)改性后的填料γ-Al_2O_3催化氧化活性较高。考察了KH560用量、水解时间、吸附时间及吸附温度对催化效果的影响。在优化条件下(2mL KH560/Et OH溶液(体积比1∶25),水解1h,吸附4h,吸附温度50℃),偶联剂对填料γ-Al_2O_3表面产生一定的包覆,在催化氧化TMB时较温和,副反应较少,TMB转化率和TMBQ选择性分别为14.3%和72.4%。     

聚苯乙烯/银纳米粒子复合微球的合成及催化性能

首先通过乳液聚合和浓硫酸酸化制备表面富含磺酸根的磺化聚苯乙烯(PS)微球(直径532 nm),再用其静电吸附[Ag(NH_3)_2]~+离子,最后采用聚乙烯吡咯烷酮还原表面吸附的[Ag(NH_3)_2]~+离子,得到了负载银纳米粒子的PS/AgNPs复合微球.采用扫描电子显微镜、透射电子显微镜、紫外-可见光谱、红外光谱和X射线衍射表征了PS/AgNPs复合微球,并考察了其对甲基蓝(MB)的催化性能.结果表明,Ag纳米粒子高度分散在磺化PS微球表面;该PS/AgNPs复合微球对催化转化MB有较高的催化活性,并可多次重复利用.本研究在催化降解有机污染物方面有一定的实用价值.     

磁性金属-有机骨架复合材料的构建及在环境中的应用

磁性金属-有机骨架(MMOFs)复合材料是一类新颖的功能材料;MMOFs在磁性功能粒子的基础上结合了金属有机骨架材料的孔径均一、比表面积高、化学和热稳定性良好、吸附亲和力强等性能,在催化和环境等领域中显示出潜在的应用前景.本文简要概述了近年来制备的MMOFs复合材料,包括磁性微球核壳结构、磁性纳米颗粒镶嵌结构、磁性颗粒无规则互混结构、磁性石墨烯基复合结构;并从环境污染物的吸附、富集和催化降解角度,重点总结了MMOFs在环境分析和环境修复中的应用.     

微乳液法制备介孔碳材料

介孔碳材料因具有高比表面积,规则的孔隙结构,低密度,良好的生物相容性及导电性,被广泛应用于催化、能量储存及转化、吸附分离和药物递送等领域。微乳液法具有制备工艺简便、环境友好、可大规模生产及产物结构可控性强等突出优势,在制备孔隙结构可控和特殊形态介孔碳方面取得突破性的进展。本文首先着重分析了微乳液法制备介孔碳的反应机理,包括微乳液诱导协同组装机制、乳液溶胀效应和微流控液滴技术。其次,进一步探讨了控制介孔碳材料孔隙形态、外部形貌及内部结构的影响因素。最后,对新型介孔碳材料在能源储存与转化、催化、吸附以及药物递送领域的应用进行了归纳,并对未来的发展提出了展望。     

石墨烯涂层在甲苯低温催化燃烧用堇青石负载Pd整体式催化剂中的作用（英文）

对于传统整体催化剂而言,堇青石等基体比表面积低,往往需先涂覆活性氧化铝等高比表面涂层,此外低温催化燃烧反应生成的水和周围空气中的水分会大量吸附于亲水性氧化物涂层表面,导致贵金属催化活性降低,同时,贵金属的分散度也是影响催化剂活性的主要因素.我们利用石墨烯高疏水性、二维平面结构、对苯环强吸附及对贵金属颗粒的高分散与锚定作用等独特性能,发展基于石墨烯涂层的高活性纳米Pd整体催化剂,以改善上述问题.所制备的Pd/石墨烯/堇青石(Pd/Gr/Cor)复合材料作为整体催化剂用于甲苯低温燃烧反应,通过考察催化性能和吸附行为,重点研究了石墨烯涂层的作用.催化性能结果表明,与无石墨烯涂层的传统Pd/Cor催化剂相比,Pd/Gr/Cor催化剂对甲苯的起燃温度从175℃降至132℃,且在水蒸气存在的情况下表现出更好的稳定性.TEM和吸水速率表征表明,石墨烯涂层可显著提高Pd纳米粒子的分散性,提高堇青石载体的疏水性.动力学研究表明,Pd/Gr/Cor催化剂上甲苯催化燃烧符合一级反应动力学规律,活化能为60.93 k J/mol.此外,研究了其吸附行为,包括吸附等温线,吸附动力学和吸附热力学.模拟结果表明,Pd/Gr/Cor催化剂对甲苯具有优异的吸附性能,对甲苯的吸附符合Freundlich模型,为化学吸附.FLm双点位吸附模型表明,石墨烯表面吸附了大量的甲苯,而Pd粒子表面吸附的甲苯相对较少,但亲和力较强.吸附热力学计算表明,石墨烯对甲苯的吸附是一个自发的放热反应,是一个熵减小的过程,表明甲苯分子可在石墨烯上高度有序组装.石墨烯与Pd之间的显著浓度差和亲和力的差距确保了反应过程中甲苯在石墨烯上的快速转移.吸附动力学研究表明,催化剂对甲苯的吸附为快速过程,催化反应为控速步骤.综上,石墨烯涂层不仅可以提高Pd纳米粒子的分散性,提高催化剂的疏水性,在催化反应过程中,还可利用其强吸附能力提高催化剂表面的甲苯浓度,而显著的浓度差和亲和力的差距可作为驱动力为Pd粒子提供甲苯,从而发挥吸附-催化协同作用优势,进一步提高催化性能.     

具有高选择性吸附的表面分子印迹磁性纤维素微球的制备与性能

以纤维素和纳米Fe₃O₄为原料制得磁性纤维素微球, 在纤维素微球表面选择合适的模板分子, 以甲基丙烯酸、 丙烯酰胺和N,N'-亚甲基双丙烯酰胺为功能单体, 采用水溶液聚合法制得表面分子印迹磁性纤维素微球. 采用傅里叶变换红外光谱(FTIR)、 X射线衍射(XRD)和振动样品磁强计(VSM)等表征了分子印迹聚合物微球的结构. 以罗丹明B(RhB)为模板分子, 通过吸附动力学与吸附热力学实验研究了表面分子印迹磁性纤维素微球对RhB的吸附性能, 结果表明, 制备的表面分子印迹磁性纤维素微球对罗丹明B具有特异性识别作用, 饱和吸附量达到0.542 mg/mg, 吸附平衡时间为10 h左右. 表面分子印迹磁性纤维素微球大大降低了对吸附环境的依赖, 并可重复利用.     

碳纳米管/活性炭复合微球的制备及其对VB12的吸附应用

采用反相乳液法制备碳纳米管/壳聚糖复合微球(CNTs/CTS), 并对其进一步炭化、活化制得碳纳米管/活性炭复合微球(CNTs/AC). 以此复合微球为吸附材料, 探索了其对中分子代表物质VB12的吸附. 研究结果表明, 碳纳米管含量70%(w)的复合微球经水蒸气适当活化后球形度好、吸附性能优异, 其对VB12的吸附量达23.59 mg·g-1, 分别是活性炭和大孔吸附树脂的5.4和2.7倍. 分析表明这是由于碳纳米管/活性炭复合微球具有发达的中孔结构.     

基于烧结微纤多孔结构材料的微反应器中的苯硝化反应

基于烧结微纤结构材料发展了一种集微混合、反应和换热于一体的微反应器,以苯硝化为模型反应考察了该微反应器用于快速、强放热的液-液两相混合反应的效果.烧结微纤材料具有大的空隙率、三维开放孔结构和大的面积与体积比,有利于传质和传热,同时微纤三维网络具有微搅拌器的作用,有利于流体的微米尺度分割和快速混合.因此,苯硝化反应得以在很短的时间内高选择性地进行完全.在一定的操作条件下,苯转化率可以达到91.7%,硝基苯选择性高达99.4%.     

利用原位微纤化技术控制聚合物形态的研究进展

综述了利用原位微纤化技术控制聚合物形态的研究进展,简要介绍了原位微纤化共混物的概念、制备方法、影响成纤的因素及常见原位微纤化体系等,讨论了原位微纤化技术对碳纳米管(CNTs)/聚碳酸酯(PC)/聚乙烯(PE)、碳黑(CB)/对苯二甲酸乙二醇酯(PET)/PE及纳米碳酸钙(nano-CaCO3)/CB/PET/PE等体系的形态调控以及体系形态与力学性能、电学性能的关系,简要介绍了原位微纤化技术在废旧塑料回收方面的应用,最后阐述了原位微纤化技术的重要性并展望了其应用前景.     

Novel microfibrous composite bed reactor: high efficiency H2 production from NH3 with potential for portable fuel cell power supplies

A novel microfibrous composite bed reactor was developed and was demonstrated for high efficiency hydrogen production by the decomposition of ammonia at moderate temperatures in portable fuel cell power system applications. By using a high-speed and low-cost papermaking technology combined with a subsequent sintering process, sinter-locked three-dimensional microfibrous networks consisting of approximately 3 vol% 8 microm (dia.) nickel microfibers were utilized to entrap approximately 35 vol% 100-200 microm dia. porous Al(2)O(3) support particulates. A CeO(2) promoter and active Ni component were then dispersed onto the pore surface of the entrapped Al(2)O(3) support particulates by a stepwise incipient wetness impregnation method. The microfibrous structure took advantage of a large void volume, entirely open structure, high heat/mass transfer, high permeability, good thermal stability, and unique form factors. Addition of ceria significantly promoted the low-temperature activity of Ni/Al(2)O(3) catalyst particulates incorporated into the micorfibrous structure. The use of fine particles of catalyst significantly attenuated the intraparticle mass transport limitations. As a result, the present novel microfibrous composite bed reactor provided excellent activity and structure stability in ammonia decomposition, as well as low pressure drop and high efficiency reactor design. At a 90% conversion of a 145 sccm ammonia feed rate, the microfibrous entrapped Ni/CeO(2)-Al(2)O(3) catalyst composite bed could provide a 4-fold reduction of catalytic bed volume and a 5-fold reduction of catalytic bed weight (or 9-fold reduction of catalyst dosage), while leading to a reduction of reaction temperature of 100 degrees C, compared to a packed bed with 2 mm dia. Ni/CeO(2)-Al(2)O(3) catalyst pellets. This composite bed was capable of producing roughly 22 W of hydrogen power, with an ammonia conversion of 99% at 600 degrees C in a bed volume of 0.5 cm(3) throughout a 100 h continuous test. These initial and promising results established that the microfibrous nickel-based catalyst composites were effective for high efficiency production of hydrogen by ammonia decomposition, while achieving a significant reduction of overall catalytic bed weight and volume. We anticipate our assay to be a new point for small-scale hydrogen production, where the microfibrous catalytic reactors considered in isolation can satisfy several of the most fundamental criteria needed for useful operation.     

Options for rapid analysis of peptides and proteins, using wide-pore, superficially porous, high-performance liquid chromatography particles with unique bonded-phase ligands

The large size and complexity of many proteins constrains the reversed-phase high-performance liquid chromatography packings that are useful for their separation. Wide-pore, superficially porous, silica-based packings with solid 4.5-microm cores and a 0.25-microm porous outer layer (Poroshell) demonstrate a variety of characteristics that are beneficial for the separation of proteins. A shorter diffusion distance allows separations of large molecules at high linear velocities. This benefit over totally porous particles is clearly shown using separations of a peptide-protein standard. The structure and reduced surface area (4.5 m2/g) of these superficially porous particles simplifies interactions with its surface, resulting in improved peak shapes and resolution. Specialized bonding chemistries for low- and high-pH operation may be used to change band-spacing and achieve atypical separations. These rapid analysis options are demonstrated using protein standards and very high molecular weight glycosylated proteins including intact monoclonal antibodies, IgM, alpha2-macroglobulin, and glycophorin. In liquid chromatography-mass spectrometry analysis of a myoglobin peptide digest, bidentate-C18-bonded superficially porous packings achieve complete runs in 4 min and demonstrate an elution pattern that is unique from that of material bonded with sterically protected C18 ligands.     

Perspective on concentration polarization effects in electrochromatographic separations

This work illustrates the appearance and electrohydrodynamic consequences of concentration polarization in the particulate and monolithic fixed beds used in capillary electrochromatography and related electrical-field assisted processes. Key property of most porous materials is the co-existence of bulk, quasi-electroneutral macroporous regions and mesoporous compartments which are ion-permselective (due to electrical double-layer overlap) causing different transport numbers for co-ionic and counterionic species, e.g., background electrolyte components, or the analytes. For a cathodic electroosmotic flow the (cation) permselectivity, together with diffusive and electrokinetic transport induces depleted and enriched concentration polarization zones at the anodic and cathodic interfaces, respectively, in dependence of the mobile phase ionic strength and applied electrical fields. At high field strength a secondary, nonequilibrium electrical double layer may be created in the depleted concentration polarization zones of a material stimulating electroosmosis of the second kind. The potential of this induced-charge electroosmosis with respect to nonlinear flow velocities and electrokinetic instability mixing (basically destroying the concentration polarization zones) is analyzed in view of the pore space morphology in random-close packings of spherical-shaped, porous particles and hierarchically structured monoliths. Possible applications based on a fine-tuning of the illustrated effects emerge for microfluidic pumping and mixing, or the intensification of sample recovery in adsorption processes. With this perspective we want to focus the attention on concentration polarization in electrochromatographic systems by presenting and discussing original data acquired on relevant microscopic as well as macroscopic scales, and point towards the importance of related effects in colloid and membrane science.*     

Multifunctional Pd/MOFs@MOFs Confined Core-Shell Catalysts with Wrinkled Surface for Selective Catalysis

Process intensification, targeting the maximization of spatial-temporal productivity utilizing minimum energy and resources has always been the constant trends especially in chemical industry. In this regard, tandem reactions that are able to perform a multi-step reaction in a single pot by eliminating costly separation steps have been viewed as a typical paradigm. However, a spatial isolation of varied active sites with a controlled manner in a single catalyst to avoid deactivation and work synergistically is a challenging problem yet sometimes being overlooked. In this work, a spatial base-metal core-shell structured catalyst with wrinkled surface was successfully fabricated by a direct homoepitaxial growth method in an acid/water system, which exhibited increased hydrophobicity, exposure of active sites and significantly improved product selectivity towards one-pot Knoevenagel condensation-hydrogenation tandem reaction compared with the uncoated catalyst. Meanwhile, the catalytic performance was largely retained and the structural stability was maintained even after successive 8 cycles, which shows great promise for industrial applications.     

Selectivity changes towards steroids in packed column supercritical fluid chromatography (SFC) induced by temperature and pressure variation

Summary Pressure/temperature variation in SFC was shown to influence selectivity towards steroids. Major changes were observed for polar column packings compared to non-polar packings and variation of the amount of modifier showed that this is valid over the whole investigated range. The effect is underlined by a fall in resolution in the low density range (low pressure/high temperature) for polar stationary phases and appears to be significantly larger than for non-polar phases. Major selectivity shifts induced by variation of the physical properties of the mobile phase are considered to be due to the greater effect of polar modifiers on the nature of polar stationary phases than on non-polar phases.     

中空纳米材料的构建原理及其在光催化制氢和二氧化碳还原反应中的应用

随着全球经济的快速发展,能源短缺与环境污染成为当今世界共同关注的热点问题,开发和利用洁净能源成为当务之急.近年,以半导体为基础的光催化技术引起了国内外的广泛关注,其中包括光催化分解水制氢、光催化还原CO2、光催化固氮以及光催化降解污染物等.尤其太阳能驱动的光催化分解水和光催化CO2还原均可将太阳能转化为可储存和运输的化...     

Selectivity in reversed-phase separations Influence of the stationary phase

The selectivity difference between 15 different stationary phases was measured using a large number of analytes at 2 or 3 different pH values (3, 7 and 10) with acetonitrile and methanol as the mobile phase modifiers. The packings discussed include standard C(8) and C(18) packings, packings with embedded polar groups, a phenyl packing, a pentafluoro-phenyl packing, an adamantylethyl packing and others. The major selectivity differences observed are discussed in detail. Specific effects such as pi-pi interactions on phenyl packings or hydrogen-bond interactions on phases with embedded polar groups are confirmed.     

Reaction of hydrogen chloride with microfibrous filtering materials

Russian Journal of Applied Chemistry - The resistance of microfibrous filtering materials based on cellulose diacetate, polystyrene, and fluoroplastic to prolonged action of high concentratoins of...     

分离蛋白质的高效强阳离子交换色谱填料的合成及性能研究

带端羟基的大孔硅胶与氯磺酸反应制得分离蛋白质的强阳离子交换色谱填料。填料分离度高,蛋白质活性回收率大于７６％,可用于蛋白质及生物工程产品的分离。     

内核含Pd的Pt基核壳结构电催化剂

燃料电池汽车已被确立为我国的战略性新兴产业,目前正处于大规模商业化的前夜,铂基电催化剂作为质子交换膜燃料电池的核心材料之一,其活性、耐久性和成本制约着这一洁净能源技术的进一步发展。高性能低铂核壳电催化剂被广泛认为有望解决这一瓶颈问题,虽然国内外在这一领域的研究取得了诸多重要的进展,但是仍存在着制备过程复杂、非铂贵金属内核尺寸较大及核壳结构宏观表征困难等问题。本文介绍两种相对简单、易放大的制备方法,即一锅法和液相合成结合区域选择原子层气相沉积法,均获得了性能优良的Pd3Au@Pt/C核壳结构电催化剂,Pd3Au内核尺寸控制在约5 nm,并利用循环伏安测试和甲酸氧化反应从宏观角度研究了铂层在内核表面的覆盖情况,探索了含钯核壳结构电催化剂的新型宏观表征方法。