介孔沸石合成方法的研究进展

系统地总结了介孔沸石的合成方法,包括对合成的沸石分子筛的后处理、硬模板法和软模板法;并就制备方法和产品结构的特点进行了评述。后处理法包括对沸石分子筛的脱铝处理、脱硅处理及热处理;硬模板主要包括碳纳米粒子、介孔碳黑、碳纳米管、碳纳米纤维、碳气凝胶、有序介孔碳、胶体复制碳、无机纳米粒子等;软模板主要包括高分子聚合物和有机硅烷模板剂。     

介孔碳微球的合成及其应用研究进展

目前,介孔碳微球的合成主要有硬模板和软模板两种方法。硬模板是将碳前驱体通过溶剂挥发填充到已合成的球形介孔材料(硬模板)中,然后热处理掉硬模板得到介孔碳微球;软模板则是以三嵌段共聚物F127做为模板剂,酚醛树脂作为碳源在水热条件下制备出介孔碳微球。介孔碳微球在超级电容、锂离子电池、气体储存、生物医药等领域获得广泛应用,然而在摩擦润滑领域的研究却未见报道。结合本课题组的前期研究提出了其在摩擦领域的研究思路并展望了其应用前景。     

多孔碳纳米片的制备及其在电化学领域的应用研究进展

介绍了二维多孔碳纳米片(PCNs)材料在能源领域的应用优势,综述了PCNs的制备方法以及在锂离子电池、超级电容器和电催化氧还原反应等电化学领域的应用研究进展。PCNs的制备方法为硬模板法(包括空间、盐粒表面和其他二维材料表面模板)、软模板法(包括使用两亲性小分子和两亲性块状共聚物(BCPs)制备PCNs)、无模板法(包括小分子、聚合物和生物质作为前驱体来制备PCNs)。其中软模板法相比硬模板法,其稳定性较差,还需进一步提高。指出未来应致力于开发制备PCNs的新方法和新型PCNs基材料,同时研究此类PCNs材料在分离膜、生化传感器、量子器件等方面的应用。     

微介孔复合分子筛的合成进展

微介孔复合分子筛是一类同时具有微孔和介孔的分子筛材料。由于含有孔径尺寸更大的介孔,所以在含大分子多的重劣质原油的催化裂化处理方面更具有优势。目前,微介孔复合分子筛的合成方法主要分为"自下而上"和"自上而下"2大类。在归纳这2类方法的基础上,进一步阐述了其中包含的一些具体方案,如硬模板剂法、软模板剂法、脱硅法、脱铝法等的制备过程及特点。     

以原位碳化蔗糖为硬模板合成多级孔道SAPO-34分子筛

为强化SAPO-34分子筛内传质过程,增强其酸性位的可接近性,以原位碳化的蔗糖为硬模板,采用双结构导向剂(四乙基氢氧化铵、吗啡啉),通过干凝胶方法合成了多级孔道SAPO-34分子筛。使用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)及氮气物理吸附对分子筛结构进行表征,并进行了低密度聚乙烯热解性能考评。结果表明,合成的多级孔道SAPO-34晶体具有纳米尺寸,含有晶内介孔,介孔体积达0.41 cm3/g。四乙基氢氧化铵具有促进成核的作用,使晶体尺寸降低。结晶过程中纳米晶体对碳模板的包裹造成了晶内介孔的形成。该分子筛在低密度聚乙烯热解反应中T50温度显著降低,说明其具有更多可接近的酸性位。     

硬模板法合成晶态介孔金属氧化物研究进展

晶态介孔金属氧化物材料因具有窄的孔径分布、大的比表面积、有序的孔道结构以及高度晶化的孔壁而在工业催化、光电等领域有着广泛的应用.在各种制备方法中,硬模板法因制备方法简单、条件温和、产物孔道结晶度高而受到了广泛关注.对硬模板法中介孔硅模板和介孔碳模板进行了介绍;总结了近年来硬模板法合成氧化铬、氧化铁、氧化铈、氧化镁和氧化钴等晶态介孔材料的研究进展;概述了该材料的发展趋势和应用前景.     

多级孔ZSM-5分子筛的合成及其金属改性研究进展

多级孔ZSM-5分子筛具有微孔分子筛良好的酸催化性能和介孔材料优异的传质扩散性能,在催化领域有着广阔的应用前景。本文综述了多级孔ZSM-5分子筛的研究进展,主要介绍了合成方法,包括后处理法、硬模板法、软模板法和无模板法,同时介绍了多级孔ZSM-5分子筛的金属改性方法,包括浸渍法、离子交换法和原位改性法。金属改性后的多级孔ZSM-5分子筛不仅可以有效减少传质阻力,而且具有独特的金属催化活性,受到了研究者的广泛关注。     

模板法制备多孔无机材料的研究进展

本文综述了近10年采用模板法制备无机多孔材料的研究进展。主要包括生物模板法．无机分子筛模板法、聚合物模板及氧化铝模板等方法,比较了各种方法的优缺点,并对多孔材料在生产实际中的应用做了介绍。     

无机介孔材料的合成研究新进展

综述了无机介孔材料的制备方法,包括软模板法和硬模板法,并对硬模板法包含的液相浸渍法、化学气相沉积法(CVD)、固相研磨法、超声波辅助法进行了详细阐述,展望了硬模板法合成介孔材料的前景。     

多级孔分子筛材料的研究进展

综述了近年来多级孔分子筛的研究进展,主要分为直接合成法和后处理法。直接合成法包括硬模板法和软模板法,后处理法包括脱铝法、脱硅法以及脱铝脱硅联用法。总结了各种处理方法的优点以及存在的问题,旨在为多级孔分子筛的制备提供更多的理论依据,并对其发展前景进行了展望。     

BETA zeolite nanowire synthesis under non-hydrothermal conditions using carbon nanotubes as template

The properties of carbon nanotubes, used as a nanometric template and as a reactor for the synthesis of BETA zeolite, have been investigated. The confinement effect of the carbon nanotubes, induced by the high aspect ratio of the tubes could be effectively used for the synthesis of one-dimensional nanowire zeolitic materials under non-hydrothermal macroscopic conditions. Zeolite material is easily recovered by combustion of the nanotubes. The average sizes of the zeolite particles are about 20 nm. The BETA zeolite was successfully used as a catalyst for benzoylation of anisol. The zeolite catalyst exhibits a high activity compared to a commercial BETA, essentially due to its high external surface area.     

The versatile synthesis method for hierarchical micro‐ and mesoporous zeolite: An embedded nanocarbon cluster approach

In this work, we are reporting for the first time the synthesis of hierarchical micro‐ and mesoporous zeolite using silica–carbon (SiO₂/C) composites prepared by pyrolysis of carbonaceous gases in the presence of silica gel. The pyrolysis effectively yielded carbon deposited onto the raw silica material. The obtained SiO₂/C composites were utilised as a bifunctional material, mesoporous template and silica source, for the zeolite synthesis. Tetrapropylammonium hydroxide (TPAOH) was used as a microporous template. The combination of the obtained composites and the TPAOH for the hydrothermal synthesis resulted in the formation of hierarchical micro‐ and mesoporous ZSM‐5. The results from the SEM, TEM, and N₂ adsorption/desorption isotherms, and ²⁷Al MAS NMR characterisations of the synthesised samples obtained after the removal of the templates confirmed the successful formation of the micro‐ and mesoporous zeolites. The mesoporosity of the zeolites could be controlled by adjusting the carbon content in the SiO₂/C composites while the carbon content could be controlled by varying the deposition time and the concentration of the carbonaceous gases used. This controllable and efficient synthesis method is considered to be a promising method for creating hierarchical micro‐ and mesoporous zeolites. © 2011 Canadian Society for Chemical Engineering     

以天然硅铝质黏土矿物为原料制备沸石分子筛及其应用

沸石分子筛是一种具有规则孔道结构的硅铝酸盐晶体,在气体吸附分离、工业催化、重金属离子污染治理等领域被广泛应用。传统沸石分子筛的水热合成常以含硅、铝的化工产品以及有机模板剂为原料,不仅价格昂贵,且污染环境。因此,开展以天然黏土为原料绿色合成沸石分子筛的相关研究,将廉价的天然黏土资源转化成高附加值的化工产品,具有重要的研究意义与经济效益。从天然黏土活化工艺、黏土基沸石合成工艺技术及相关机理等方面介绍了黏土基沸石分子筛的研究进展,重点综述了黏土基沸石分子筛作为工业固体酸催化剂、气体吸附分离反应器及重金属吸附剂的应用,并对黏土基沸石分子筛的未来发展趋势进行了展望。     

ZSM-35沸石原位固相转化法合成过程控制

以乙二胺(EDA)为模板剂,采用原位固相转化法合成了ZSM-35沸石,并通过XRD对沸石晶化过程中的影响因素和晶化机理作了详细考察。结果表明,制备ZSM-35沸石适宜的硅铝摩尔比为21n(SiO2)/n(Al2O3)37;Na+与模板剂EDA协同作用,共同对ZSM-35沸石起着结构导向作用;延长晶化时间,ZSM-35沸石容易向ZSM-5沸石转晶,合成ZSM-35沸石合适的晶化时间为14～21 h。对晶化机理的考察表明ZSM-35沸石的合成过程具有固相机理的特征,并且由于ZSM-35沸石与ZSM-5沸石具有相同的次级结构单元,在晶化过程中容易发生转晶。     

Synthesis of ordered carbon replicas by using Y-zeolite as template in a batch reactor

Ordered carbon material that preserves the structural regularity of the parent zeolite template was synthesized by using ethylene as carbon source and HY-zeolite in a batch reactor. The obtained carbons exhibit a high degree of microporosity having BET surface areas between 1400 and 2400 m²/g. The morphology and structure of the prepared carbon materials were investigated by elemental analysis, X-ray diffraction measurements, scanning electron microscopy and nitrogen adsorption. The results were compared with the parent zeolite template. The carbonization procedure of precursor-encapsulated samples was investigated by thermal analysis and it has been found that the resulting quality of the ordered carbons strongly depends on the heat treatment of the composite material.     

以稻壳为原料合成等级孔Y型分子筛

以稻壳为原料,通过高温碱活化提取稻壳中的硅作为分子筛合成的硅源,利用碳化稻壳中的碳作为介孔模板合成具有等级孔结构的Y型分子筛。采用XRD、N_2吸附-脱附等表征合成的Y型分子筛。考察碱度、晶化时间、晶化温度等合成条件对Y型分子筛结构特性的影响。结果表明,随着碱度的增加,分子筛结晶度先增加后降低。碱度为6.66时,合成的Y型分子筛结晶度最高。当晶化温度为90℃、时间为16 h时,合成的分子筛中含有较少的杂晶。     

ZSM-22分子筛的合成与表征

以1,6-己二胺（DAH）为模版剂,在水热合成条件下考察了合成方法、添加晶源、不同硅源、晶化温度、硅铝比等因素对合成ZSM-22分子筛的影响。并采用XRD、SEM等方法对合成样品进行了表征。实验结果表明,在晶化温度为433 K、原料配比为90（SiO2）∶1（Al2O3）∶27（DAH）∶27（K2O）∶3 600（H2O）时,采用正硅酸乙酯为硅源,以动态合成法可合成结晶度良好的ZSM-22分子筛。     

模板剂在ZSM-5分子筛合成中的应用

分析了模板剂在合成ZSM-5分子筛中的作用机理,在总结常用ZSM-5分子筛模板剂的基础上,系统阐述了模板剂对ZSM-5分子筛的粒径大小、结晶度和晶体形态的影响,最后探讨了混合模板剂在ZSM-5分子筛合成中的应用。     

Carbon spheres prepared from zeolite Beta beads

Porous carbon beads were prepared from macroporous anion-exchange resin beads preliminary converted into resin-zeolite Beta composite or pure zeolite Beta spheres. Two synthesis procedures were used depending on the initial template employed. In a series of experiments, the resin from the resin-zeolite Beta composite was directly carbonized into carbon. In another series of experiments, the resin was removed by oxidation at 600 °C leaving behind self-bonded zeolite Beta beads, which were filled with carbon by chemical vapor deposition (CVD) of propylene. As a final step for both procedures, the zeolite was dissolved in hydrofluoric acid. All the carbons prepared inherited the macroscopic spherical shape of the template spheres as well as the morphology of the primary particles building up the beads. The synthesis procedure and the carbonization temperature or the temperature for CVD of carbon employed influenced the ordering and the pore structure of the produced carbons. The carbons prepared by direct carbonization showed relatively low surface areas, less than 1000 m² g⁻¹, and no zeolite structural regularity. The samples obtained via CVD maintained the zeolite ordering with a periodicity of 11.7 Å and had surface areas of over 2000 m² g⁻¹.     

Synthesis methods for preparing microporous carbons with a structural regularity of zeolite Y

As reported in previous communications, novel porous carbons were synthesized by using zeolite Y as a template. The carbons possess a periodic ordering structure and high BET surface area with large micropore volume. In this work, the details of the synthesis methods for preparing the ordered microporous carbons were examined. It was found that the following two-step process, the filling of carbon into zeolite channels by impregnation of furfuryl alcohol and then chemical vapor deposition (CVD) of propylene, was indispensable for preparing carbon with highly periodic ordering. In addition, low-temperature CVD and the further heat treatment of zeolite/carbon composite after the CVD are key points for the appearance of both good long-range periodicity and very high BET surface area with almost no mesoporosity in the carbons.