软模板导向合成多级孔丝光沸石及其苯的苄基化催化性能

通常认为丝光沸石是具有一维孔道结构的微孔沸石, 在涉及大分子的催化反应中存在较为严重的扩散限制。以双季铵型表面活性剂C₁₈H₃₇N⁺(CH₃)₂C₆H₁₂N⁺(CH₃)₂C₆H₁₃(Br^-)₂(C_18-6-6Br₂)作为软模板, 在水热条件下制备了多级孔丝光沸石分子筛。采用XRD、FT-IR、SEM、TEM、TG-DTG、N₂物理吸附、NH₃-TPD等手段对样品的晶体结构和物化性能进行了表征。结果表明, 加入C_18-6-6Br₂制备了纳米棒定向排列的多级孔丝光沸石, 而且可通过改变合成体系中C_18-6-6Br₂/SiO₂的比值, 对样品的晶粒尺寸、介孔表面积和介孔孔容进行系统调变。在苯与苯甲醇的苄基化反应中, 多级孔样品比传统微孔丝光沸石表现出更好的苄基化反应催化性能和显著提高的反应速率。多级孔丝光沸石优异的催化性能归因于介孔的存在使其具有更多的可接近活性位和更优异的质量传输性质, 这种独特的多级孔丝光沸石在大分子催化转化反应中具有较大的应用潜力。     

饱和ATP为原料合成多级孔ZSM-5沸石分子筛的制备与表征

研究以饱和ATP吸附材料为合成沸石分子筛的硅源,采用双模板法,用四丙基氢氧化铵(TPAOH)为微孔模板剂和十六烷基三甲基溴化烷(CTAB)为介孔模板剂直接合成多级孔ZSM-5沸石分子筛,通过XRD、SE M、比表面积及孔径分析仪进行N_2吸附-脱附等手段对多级孔ZSM-5沸石分子筛表征测试分析。结果表明:饱和ATP吸附材料在180℃下,水热提纯12 h获得硅源,再加入TPAOH和CTAB进行初始凝胶反应,后移入水热反应釜中,控温180℃,水热晶化反应15 h,即得多级孔ZSM-5沸石分子筛。     

多级孔沸石的孔结构调控合成及其催化应用研究进展

沸石由于特殊的离子交换性, 丰富的酸性位以及较高的水热稳定性, 被广泛地应用于工业催化和分离吸附等领域。但是由于其较小的微孔尺寸(< 1.5 nm), 在一些大分子参与的催化反应中受到极大的限制。多级孔沸石在保留传统沸石晶化骨架、酸性位以及高水热稳定性的同时引入了多级孔结构, 可极大改善分子的扩散和传质, 减少积碳, 延长催化剂的使用寿命, 使其在催化领域获得更为广泛的应用。本文系统综述了多级孔沸石在孔结构调控方面的研究进展, 着重介绍了无序介孔/大孔结构的多级孔沸石、有序介孔结构的多级孔沸石、取向排列的双介孔结构多级孔沸石、空心结构的多级孔沸石、集大孔-介孔-微孔为一体的多级孔沸石等的合成策略与机理以及结构表征。概述了多级孔沸石在催化领域中的应用进展; 通过与传统沸石和无定型介孔材料的对比, 这种新型的多级孔沸石展现出独特的优势。最后, 对未来多级孔沸石的发展与应用潜力进行了展望。     

以聚乙二醇为模板凝胶转化制备介孔ZSM-5沸石及其催化性能

以聚乙二醇为介孔导向剂, 通过凝胶转化制备了介孔ZSM-5沸石。研究表明, 在TPA⁺/SiO₂=0.1时经过9~15 h溶剂挥发制得的凝胶, 在160℃处理24 h可得到介孔ZSM-5沸石; 挥发时间太短或太长会得到纯的ZSM-5沸石或介孔材料, 说明在凝胶的制备过程中, 通过控制溶剂的挥发程度, 既可为沸石生长过程提供所需的水分, 又能避免沸石晶体形成过程中无定型相的产生, 从而在较低的TPA⁺浓度下获得介孔ZSM-5沸石。与传统的ZSM-5沸石相比, 利用该方法制备的介孔ZSM-5沸石不仅具有微孔/介孔多级孔结构, 同时具有沸石材料较强的酸性、较高的水热稳定性和择形催化性能, 使其在苯甲醛与正丁醇的大分子醇醛缩聚反应中能有效地克服传统沸石孔径限制的缺点, 收率高达42.4%。     

CTAB对多级孔分子筛合成及孔道层次结构影响

以预处理后的凹凸棒石(Si-ATP)为前驱体, 采用双模板剂一步法合成了多级孔分子筛, 研究了结构导向剂十六烷基三甲基溴化铵(CTAB)用量对分子筛孔道层次结构和种类的影响。结果表明：当CTAB用量为0.01~0.03 g 或0.05~0.07 g时, 孔道层次结构因子(HF)与CTAB用量呈线性相关; XRD结果显示, 当CTAB用量为0.03~0.05 g时, 分子筛从ZSM-5型向(H)ZSM-11型转变, 这说明在利用此方法制备多级孔分子筛时, 可通过调变CTAB用量定向调控分子筛微介孔比例。CTAB用量为0.05 g, 合成的(H)ZSM-11分子筛比表面积(S_BET)为432.02 m²/g, 总孔体积(V_tot)为0.40 cm³/g, 亚甲基蓝(MB)的吸附容量为366.45 mg/g, 说明CTAB导向构筑的介孔孔道有利于吸附大分子物质。     

沸石矿模板炭的制备及其纳米孔的形成机理

分别以沸石矿和人造沸石为模板、蔗糖为碳源、采用模板法制备了多孔炭材料。采用SEM和N2吸附对样品进行了表征。结果表明,沸石矿模板炭的比表面积(1070m2/g)比人造沸石模板炭的比表面积(1820m2/g)低,但沸石矿模板炭的总孔容(1.39cm3/g)和中孔孔容(0.98cm3/g)均明显高于人造沸石模板炭的总孔容(1.02cm3/g)和中孔孔容(0.39cm3/g)。沸石矿模板炭的纳米孔主要由三部分孔组成,即复制模板壁厚的“复制孔”、继承模板孔道的“继承孔”和炭化过程中形成的纳米孔。     

模板法制备介孔VN纳米电极材料及其电容性能

以十六烷基三甲基溴化铵(CTAB)为模板剂, 通过高温氨解还原V₂O₅前驱体制得了具有丰富介孔的VN纳米材料, 采用XRD与TEM分析观察样品的结构和形貌, 用N2吸附测试样品的比表面积和孔径分布. XRD分析表明, 介孔VN纳米材料属于立方晶系的晶体结构. TEM和N₂吸附测试结果表明, VN纳米材料的颗粒粒径大约为10 nm, 比表面积为88 m²/g, 有比较丰富的2~6 nm的介孔. 在1 mol/L KOH电解液中进行循环伏安和恒流充放电测试研究其电容性能, 结果显示, VN电极同时具有双电层电容性能和氧化–还原反应的准电容性能, 1 mV/s的扫描速率下能获得517 F/g的比电容; 当扫描速率增大到10 mV/s时, 其比电容仍有275 F/g.     

染料敏化太阳电池多级孔炭对电极的制备及性能研究

以F127为模板剂, 采用自组装与后活化相结合制备了具有微孔-介孔结构的多级孔炭. N2吸附等温线分析表明后活化可在介孔炭孔壁上生成大量微孔. 电化学阻抗谱测量表明多级孔炭电极对I₃^-还原反应的催化活性明显高于介孔炭电极, 电荷迁跃电阻为0.3 Ω·cm². 多级孔炭电极催化活性高是由于它具有较高的比表面和特殊的多级孔结构, 有效比表面积较高. 以多级孔炭电极为对电极组装染料敏化太阳电池, 电池的短路电流密度、开路电压和填充因子分别为0.624V、15.44 mA/cm²和0.67, 相应的光电转换效率为6.48%, 比介孔炭对电极电池的光电转换效率提高了11.5%.     

多级孔炭电极材料的制备及其性能研究

以聚醚F127、间苯三酚和甲醛为原料,采用KOH活化法制备出具有介孔、微孔的多级孔炭材料,利用BET、XRD、SEM对样品的组成和结构进行了表征.结果表明:随着升温速率的增加和炭化时间的减少,介孔炭材料的比表面积、孔容以及介孔表面积先增大后减小.10℃/min条件下可获得最优性能的介孔炭,其介孔表面积为324.47m2...     

埃洛石原料无模板法制备高比表面积介孔氧化硅及其在亚甲基蓝吸附中的应用

采用无模板法, 以天然的矿物原料制备介孔材料是一种经济有效的制备方法。本研究利用“煅烧-沸石化-酸处理”工艺制备高比表面积的介孔氧化硅颗粒。研究发现,通过长时间的碱处理将煅烧埃洛石转化为沸石,随后通过酸处理,可制备出比表面积高达767 m²/g的介孔氧化硅材料。该工艺机理为: 850℃煅烧使埃洛石转变为无定型态的Si-O-Al网络结构,煅烧埃洛石在长时间的水热碱处理过程中转化为结晶态的LTA沸石硅铝酸钠,在随后的强酸性环境下,沸石的Al-O和Na-O成分被完全溶解,而残余的Si-O纳米碎片在酸环境中相互聚合,生成无定形态的介孔氧化硅颗粒。本实验制备的介孔氧化硅比表面积高达767 m²/g,最可几孔径为5 nm,其亚甲基蓝平衡吸附量可达741 mg/g,表明其在污染物吸附中具有良好的应用潜力。     

Study of synthesis of mordenite zeolite/MIL-101 (Cr) metal–organic framework compounds with various methods as bi-functional adsorbent

In the present study, for the first time the preparation of mordenite zeolite/MIL-101(Cr) metal – organic framework (MOF) samples (MOR/MIL-101(Cr)) with different methods was suggested. The preparation of compounds was performed via hydrothermal (H), solvothermal (S) and refluxing methods. The properties of synthesized compounds and individual MOF and MOR zeolite were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption–desorption measurement and thermo gravimetric analysis (TGA). The XRD results indicated diffraction peaks for each two compounds (MOR and MIL-101) in synthesized samples. The SEM and TEM images showed mixture of MOF and mordenite zeolite via refluxing and solvothermal method. In hydrothermal method, a new composite were fabricated by diffuse of MIL-101 particles with octahedral and spherical morphology in plate shaped MOR zeolite. The nitrogen sorption isotherms characterized microporous cages in MOR/MIL-101 samples and individual samples. The BET results showed the surface areas of all synthesized compounds were smaller than individual MOF and MOR zeolite. Based on TGA plots, synthesized MOR/MOF compounds were more thermally stable compared to the isolated MIL-101(Cr). All prepared compounds were tested as bi-functional adsorbent in removal of acidic/anionic methyl orange (MO) and cationic methylene blue (MB) dyes simultaneously. The acidity from framework Al-O(H)-Si sites in MOR and basicity from amine groups in MIL-101 obtained by post-synthetic modification. Among the synthesized compounds, MOR/MIL-101 composite by solvothermal method were selected as the best bi-functional adsorbent.     

Generation of mesoporosity in MOR zeolites synthesized under perturbation conditions

The hydrothermal synthesis of various mesoporous materials with mordenite (MOR) structures is performed under perturbation conditions involving varying-temperature crystallizations and the use of ternary organic templates, and at least three types of mesoporous materials are obtained from the same starting gel containing the ternary organic templates. The greater structural diversities of these materials are found to correlate remarkably with the second-staged crystallization temperature and time. Among these materials, the two mesoporous materials crystallized incompletely over low temperature periods are differently structural composites consisting of MOR crystallites within disordered mesoporous phases, whereas the mesoporous mordenite crystallized completely over relatively high temperature period possesses the intrinsic microporosity and hierarchical mesoporosity. TEM morphological investigations on the mesoporous mordenite crystals demonstrate the formation of intracrystalline mesopores. Furthermore, an entirely new approach to synthesize mesoporous MOR zeolites is proposed based on the pore-inducing role of MOR structure defects and the adequate perturbation towards synthesis conditions.     

Synthesis of stacked spherical hierarchical SAPO-34 zeolite and its methanol to olefin catalytic performance

In this paper, stacked spherical hierarchical SAPO-34 zeolite was synthesized by hydrothermal crystallization with tetraethylammonium hydroxide (TEAOH) and morpholine (MOR) as composite template by adding cetyltrimethylammonium bromide (CTAB) as mesoporogen and crystal growth inhibitor. The effects of different templates and CTAB amount on SAPO-34 zeolite was investigated by XRD, SEM, NH₃-TPD, and BET. The results showed that hierarchical SAPO-34 zeolite with high MTO catalytic performance was synthesized. With the increase amount of CTAB, the morphology of SAPO-34 zeolite changed from cubic to stacked spherical. Furthermore, the use of composite template could also greatly reduce the synthesis cost of SAPO-34 zeolite, which was of significance for its industrial development.     

聚乙二醇聚合度对介孔η-Al2O3纤维形貌及吸附能力的影响

分别以2种不同聚合度的聚乙二醇（PEG）PEG600和PEG2000为模板导向剂,采用水热法合成η-Al₂O₃（PEG600）和η-Al₂O₃（PEG2000）介孔纤维,借助XRD、TEM和N₂吸附测试对材料进行表征,研究了PEG聚合度对介孔η-Al₂O₃纤维性质的影响。通过静态吸附平衡实验考察了介孔η-Al₂O₃纤维对亚甲基蓝的吸附特性。结果表明：2种模板导向剂均可用于合成介孔η-Al₂O₃纤维。PEG聚合度对介孔结构、比表面积、孔体积和孔径有较大影响。η-Al₂O₃（PEG600）的比表面积和孔体积分别为189.899 m²·g^-1和0.329 cm³·g^-1,分别是η-Al₂O₃（PEG2000）的1.4倍和1.2倍,平均孔径也比η-Al₂O₃（PEG2000）的大。2种介孔η-Al₂O₃纤维对亚甲基蓝的吸附机制均为多分子层吸附。根据BET多层分子吸附方程计算得η-Al₂O₃（PEG600）和η-Al₂O₃（PEG2000）对亚甲基蓝的平衡吸附量分别为256.391 3 mg·g^-1和204.045 9 mg·g^-1。     

Modern synthesis strategies for hierarchical zeolites: Bottom-up versus top-down strategies

Zeolites are well known for their ordered microporous networks, good hydrothermal stability, large surface area, high acidity and selectivity. These excellent properties make zeolites extremely useful for petrochemical processes and refining. However, the presence of only microporous channels also restricts the diffusion of reactants and products into and out of the microporous networks, especially limiting zeolite applications involving bulky molecules. The importance of developing hierarchical zeolites has attracted great attention in recent years due to the prospect of increased accessibility for bulky molecules. Introducing additional mesoporosity, and even macroporosity, into conventional zeolites produces a combination of three different size scales of porosity. It expands the original zeolite hierarchical structure and greatly enhances the mass transport of molecules while maintaining the intrinsic size, shape and transition state selectivity of zeolite. The promising applications of this new zeolite architecture have prompted a multitude of efforts to develop a variety of different synthesis strategies. In this review, we summarized and evaluated the modern synthesis strategies (bottom-up and top-down) for introducing additional meso/macroporosity into microporous zeolites. The advantages and limitations of these different strategies were discussed in detail.     

中空介孔SiO2的合成及其对CrⅥ的吸附

以3-氨基苯酚/甲醛(AF)树脂为软模板、正硅酸乙酯(TEOS)为硅源、十六烷基三甲基溴化铵(CTAB)为制孔剂,采用一锅溶胶-凝胶法制备中空介孔二氧化硅(HMS)微球。通过改变反应温度对软模板AF树脂的结构以及TEOS的水解速率进行调控,制备多形貌SiO₂微球。使用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N₂吸附-脱附比表面积分析(BET)及傅里叶变换红外光谱(FTIR)等手段对制得的SiO₂微球进行表征。结果表明,随着反应温度从0℃提高到100℃,制备的SiO₂微球分别为实心微球、蛋黄壳空心球、单层壳空心球和破碎实心球等。其中具有蛋黄壳结构的HMS微球具有较大的比表面积和孔体积,比表面积可达513 m²/g,孔体积达0.432 cm³/g,孔径均匀达3.66 nm。将在30℃下制得的具有蛋黄壳结构的HMS微球表面进行接枝聚丙烯腈并偕胺肟化的改性制备蛋黄壳HMS接枝聚偕胺肟(HMS-g-PAO)。将HMS-g-PAO用于对水中Cr^Ⅵ的吸附,在pH = 2时HMS-g-PAO粒子对100 mg/mL的重铬酸钾溶液中Cr^Ⅵ有很好的吸附效果,其吸附量达140 mg/g。     

中孔FAU型沸石的合成及孔结构表征

本研究采用有机硅烷偶联剂二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵(TPOAC)作为中孔模板剂, 在水热条件下合成了具有FAU结构的中孔X和Y型沸石, 并用X射线衍射、扫描电镜、透射电镜、氮气吸附/脱附和热重分析技术对合成样品进行了结构表征。结果表明, 在该沸石合成体系中TPOAC的加入使沸石晶粒纳米化, 同时可在沸石晶粒内部创造丰富的直径为5~6 nm的中孔, 并且改变了沸石晶体的外观形貌。从而获得了不仅保持沸石固有微孔、同时具有晶内中孔和晶间中孔的介孔FAU沸石。