分子筛基复合材料的合成及应用研究进展

Research progress on synthesis and application of zeolite⁃based composites

摘要

传统分子筛存在传质阻力大，吸附量有限等问题，将其与活性炭、硅藻土等复合，形成具有协同作用的复合材料，是满足多元化需求、拓展应用领域的重要途径。本文围绕复合分子筛、分子筛-客体材料复合材料两个方面评介分子筛基复合材料制备方法的研究进展，梳理其在吸附分离、催化等领域的应用。结果表明：复合分子筛常用的合成策略有模板法、溶胶-凝胶法和分子筛硅源法等，但得到的复合材料结构不稳定，易发生相分离。分子筛-客体材料复合材料的合成方法多样，其中的静电自组装法和溶液共混法可实现与多种类型客体材料组合使用，但存在过程复杂、溶剂依赖性强等问题。尽管分子筛基复合材料在吸附分离、工业催化方面应用前景广阔，但其在气相有机污染物（尤其是VOCs）吸附中的研究仍显不足。未来研究应重点开发温和、环保的合成策略，包括但不限于低温低压合成方法、环保型溶剂体系等，以推动分子筛基复合材料的实际应用。

Abstract

The traditional zeolite with high mass transfer resistance and limited adsorption capacity， limits its application. Combining zeolite with activated carbon， diatomite， and other materials to construct composite materials with synergistic effects is the important technical ways to meet diversified needs and expand application fields. This paper conducted a critical survey on the research progress in synthesis method of zeolite-based composites， focusing on two aspects： composite zeolites and zeolite-guest material composites， and then summarized their applications in adsorption separation， catalysis， and other fields. The results showed that common synthesis strategies of composite zeolites comprise template method， sol-gel method， and zeolite silicon source method， but had disadvantages in structural instability of composites. Among these synthesis methods of zeolite-guest material composites， electrostatic self-assembly and solution blending methods can be used in combination with various types of guest materials， were promising approach to preparing zeolite- guest material composites. Meanwhile， they had disadvantages in complex processes and high solvent dependence. Despite the broad application prospects of zeolite-based composite materials in adsorption separation and industrial catalysis， research on their adsorption of gaseous organic pollutants， especially VOCs， remains limited. Universal synthesis strategies under mild conditions， such as low-temperature and low-pressure synthesis methods， as well as environmentally friendly solvent systems， should be developed in the future to promote the practical application of zeolite-based composites.

Graphical abstract

关键词

分子筛 / 复合材料 / 合成 / 应用 / 进展

Key words

zeolites / composite / synthesis / application / progress

0 引 言

沸石分子筛（也称“分子筛”）是一种具有高度有序孔结构的微孔晶体铝硅酸盐，具有多变的孔道结构（尺寸、维度以及连通性）和独特的笼结构，较高的比表面积、可调的酸度和极性、良好的水热稳定性和热稳定性等优点，在吸附分离、工业催化、生物质转化、燃料电池、热能储存等领域具有广泛的应用前景^［1-3］。

近年来，随着新型污染物等有害物质的进一步发现，利用分子筛来解决这些问题变得力不从心。例如，传统分子筛的孔道结构主要为微孔，不利于吸附质在孔道中扩散传质，且吸附有机物后脱附再生非常困难，在长期使用中容易出现结焦和积碳现象，导致孔道堵塞、失活；当反应物或客体分子超出分子筛孔道尺寸时，会使较大分子反应物难以进入分子筛的孔道中，从而降低整体反应和/或吸附速率和活性位点的可及性，严重影响其吸附、催化等性能^［4］。同时，由于分子筛晶穴中存在较强的库仑场和极性，容易吸附极性强、极化率大的污染物，对非极性物质的吸附不理想^［5］。此外，目前制备的分子筛多为粉体材料，其较小的颗粒尺寸导致“纳米效应”显著，在制备和使用过程中易出现“团聚”行为，不利于其性能的充分发挥^［6］。为拓展分子筛的应用范围或提高其性能，有研究者将分子筛与分子筛、硅藻土、活性炭、聚合物等共同制备成复合材料^［7-10］，在提高其吸附扩散性能的同时并经协同作用形成更多吸附/催化位点以增强分子筛吸附/催化性能。由于分子筛基复合材料的相关性能受形成过程的影响很大，研究各种分子筛基复合材料的形成过程具有重要意义。

本文对分子筛基复合材料的合成策略和应用的最新进展进行系统的文献调研，按照分子筛与分子筛复合、分子筛与客体材料复合两条路线对迄今为止分子筛基复合材料的制备方法进行梳理、分析、比较其优缺点，以期准确把握分子筛基复合材料制备过程中的关键点与难点，获得相对温和条件下构建分子筛基复合材料的普适性策略。同时，对分子筛基复合材料应用情况进行调研，总结了其在应用过程中存在的局限性，并为分子筛基复合材料未来的发展方向提供见解。

1 分子筛基复合材料的类型及制备方法

分子筛基复合材料是指以分子筛为基体，与其他具有特定功能的组分（第二组分）相结合形成的二元复合材料。复合材料中的不同组分可有效引入多功能性和协同效应，不仅增强了单种分子筛材料的原有性能，还拓展了其性质和功能。根据添加第二组分的不同，分子筛基复合材料可分为分子筛-分子筛复合材料（复合分子筛）、分子筛-活性炭复合材料、分子筛-硅藻土复合材料和分子筛-聚合物复合材料。

1.1　复合分子筛

复合分子筛是由两种或多种类型的分子筛通过物理或化学方法形成的复合晶体材料。根据分子筛之间复合方式的不同，复合分子筛可分为传统复合分子筛和核壳结构复合分子筛两种类型，如图1所示^{［11，12］}。传统复合分子筛通过物理混合或化学反应将两种或多种不同类型的分子筛结合在一起，形成具有多级孔结构和多种特性的复合材料。核壳结构复合分子筛是以一种特定的单晶分子筛为核心，在其表面生长一层或多层不同种类（或同种类但具有不同特性）的分子筛外壳。两种类型复合分子筛的侧重点和适用的应用有所不同，应根据研究对象和目的确定复合策略。

1.1.1　传统复合分子筛

Kokotailo等^［13］首次报道了ZSM-5-ZSM-11复合分子筛的合成，此后迅速发展。迄今，已经实现不同类型复合分子筛构建，主要包括不同种类的微孔复合分子筛^［14-16］、微-介孔复合分子筛^［17-19］及微-大孔复合分子筛^{［20， 21］}等，其在工业催化、吸附等领域展现出巨大的应用潜力。传统复合分子筛中两种材料之间存在明显的连接界面（过渡层），Ｘ射线衍射（XRD）表征结果会同时出现两种材料各自对应的衍射峰。依具体制备过程差异，传统复合分子筛的主要合成策略可分为：原位合成法和后合成法。原位合成法是通过控制合成条件进行两步结晶，在同一个反应系统中同步生成两种不同类型的分子筛，根据所用模板剂数量不同可分为单模板合成法和双模板合成法。后合成法指首先合成一种分子筛或含分子筛次级结构单元的凝胶分子筛做前驱体，然后在此基础上生长出另一种类型的分子筛，两种分子筛不在同一反应体系中生成。根据合成方法的不同可分为附晶生长法、两步晶化法、分子筛硅源法与纳米组装法。

表1总结了两种制备方法的优缺点及应用实例。与原位合成法相比，后合成法可以得到结构更复杂的复合分子筛，适用于多种分子筛组合，是目前制备传统复合分子筛的主要合成手段。需要指出的是，在使用后合成法制备复合分子筛时，有两个难点：①需要强化新生成的分子筛与原始分子筛之间的界面结合；②工艺流程待简化，以实现更绿色、经济和高效的合成路线。此外，虽然还有其他制备方法，如物理混合法^［22］、气相传输法^［23］等，但由于需要特定的设备或所得复合分子筛两相混合不均匀、强度低、性能差等问题，这些方法不常用。

1.1.2　核壳结构复合分子筛

传统复合分子筛通过两种不同孔道结构的分子筛进行复合，但难以精确控制各组分的分布和相互作用，形成的结构往往缺乏有序性，容易堵塞孔道并破坏分子筛的晶体结构。相比之下，以单晶分子筛为核心（核），在其表面均匀地包裹一层或多层不同性质或组成的分子筛壳层制备的核壳结构复合分子筛具有更清晰有序的孔道结构，可以为反应路径提供精确的导向，增强不同活性位点间的协同效应，提升材料的整体效能^{［38， 39］}。早期，由于合成技术的限制，核壳结构复合分子筛的研究主要集中在具有相同拓扑结构的核壳相，如MFI@MFI^［40-42］、TON@TON^［43］。然而，由于内核和外壳在化学组成和结构上的相似性，其无法满足多样化的应用需求。尽管相同拓扑结构核壳复合分子筛存在明显的局限性，但由于其相对简单的构建过程、相对较低的经济成本以及便于针对特定应用进行深入研究的特点，至今仍受到人们的广泛关注和研究^［44-48］。

为解决相同拓扑结构核壳复合分子筛在应对不同化学和物理需求的工业应用中存在结构单一，材料性能差等问题，研究人员开始探索合成具有不同拓扑结构的核壳复合分子筛，通过结合不同分子筛的特性，增强材料的多功能性和优化其性能以拓宽其应用领域。然而，不同拓扑结构的核壳复合分子筛的合成由于化学相容性和电荷匹配问题而更为复杂。为此，研究者通过优化现有合成方法或开发新的合成方法和设计策略，以实现特定晶型的控制合成。Wang等^［49］在传统水热结晶方法的基础上，借助ZSM-5种子对预涂MCM-41壳层进行原位固-固转化，得到了分层核壳结构的SAPO-34@ZSM-5复合分子筛，如图2所示。该方法有效克服了核心晶体与壳沸石在合成过程中的化学和结构不相容性，核-壳间的MCM-41界面更是确保了核壳结构的完整性。

为了对不同拓扑结构核壳复合分子筛有更直观的了解，对部分参考文献中的制备方法及结构特征进行了总结，见表2。目前核壳结构复合分子筛的制备主要有离子交换法、包埋法及溶胶-凝胶法等。离子交换法是将一种分子筛与另一种分子筛的模板剂进行离子交换，然后再加入分子筛合成液中经水热过程得到复合分子筛。该方法制备过程中离子交换速率和程度难以精确控制，影响复合材料的一致性和重复性。包埋法是将内核分子筛（或其分散体）分散到溶液中后加入壳层分子筛的反应母液中，通过控制工艺参数使外壳在内核表面形成。这种方法可以更好地控制核壳界面的形成和外壳的厚度，有利于实现特定功能，但壳层分子筛的生长速度和方向的严格调控，造成该方法对工艺条件要求严格，需选择合适的反应条件。相较于离子交换法和包埋法，溶胶-凝胶法由于其温和的反应条件、良好的分散性和均匀性以及对原料比例、水解和聚合过程的高度可调性等优点受到了广泛关注。虽然溶胶-凝胶法在应用过程中还存在一定的缺陷，如周期长、成本高等，但其仍是制备具有复杂结构和多功能性核壳复合分子筛的首要合成手段，未来可以不断进行工艺优化或探索更具普适性的合成方法。

1.2　分子筛-硅藻土复合材料

硅藻土是由硅藻生物的遗骸经沉积堆积后形成的生物沉积岩，其化学成分以无定型的二氧化硅（SiO₂）为主，具有大孔结构丰富和比表面积高、结构稳定、表面活性高和轻质、无毒、耐热、耐酸、储量丰富且价廉等优点，被广泛应用于石油化工、环境、食品、建筑等领域^{［62， 63］}。因此，将分子筛与硅藻土组合制备复合材料可以有效改善分子筛的窄微孔结构，提高传质和扩散过程的效率，从而提高吸附效率。另外，硅藻土中丰富的SiO₂还可以作为沸石生长的廉价无机硅源，降低复合材料的制备成本。

Liu等^［64-66］和Liu等^［67］使用机械混合法制备了硅酸钛-1（TS-1）-硅藻土复合材料，其对苯酚和甲苯的羟基化具有良好的催化性能。然而，表征发现分子筛和硅藻土相互混杂，各组分独立发挥作用，且复合材料的机械强度较低，容易破碎，无法应用到实际生产中。Anderson等^［68］发现采用水热法能有效改善硅藻土和分子筛之间界面结合力弱的问题。然而，硅藻土的大孔结构被过度生长的沸石晶体堵塞，影响吸附质在孔道内的扩散。在此基础上，Jia等^［69］通过蒸汽辅助在硅藻土表面原位生长分子筛，制备了MFI分子筛-硅藻土复合材料。虽缓解了硅藻土堵孔现象，但分子筛与硅藻土结合不牢的问题仍存在。研究表明：硅藻土和分子筛在碱性溶液中都带负电荷，静电斥力的存在影响二者结合^{［70， 71］}，这或是导致分子筛在硅藻土上负载量低且结合力弱的根本原因。

改变硅藻土的表面电荷，使其在碱性溶液中带正电荷或是解决上述问题的有效途径。Wang等^［72］首次使用逐层静电组装技术，通过静电引力将分子筛组装至硅藻土表面，但分子筛的负载量仍较低（10%）。在此基础上，Wang等^［73］引入气相传输法（VPT），经过10 dVPT水热处理后，分子筛负载量提高至51.4%，但该制备方法反应周期长，合成条件苛刻，且制备步骤烦琐，难以工业化应用，需进一步探索分子筛/硅藻土复合材料合成的新方法。已有研究表明：季铵盐型阳离子表面活性剂能有效提升多孔材料在碱性溶液中带正电荷的能力，有望提高分子筛在硅藻土上的负载量和负载的均一性。

众多学者以硅藻土为载体，以季铵盐为媒介，耦合原位生长法/二次生长法成功制备出了纳米纯硅分子筛（Silicalite-1）-硅藻土复合材料^{［74， 75］}（图3）、TS-1-硅藻土复合材料^［76］、MFI分子筛-硅藻土复合材料^{［77， 78］}及β分子筛-硅藻土复合材料^［79］。表征结果表明：这些复合材料既具有沸石分子筛的规则微孔结构，也具有硅藻土的大/介孔结构，制备的复合材料对各种污染物（苯、甲苯、乙酸乙酯、亚甲基蓝、丙酮等）相较于单种分子筛表现出更优异的吸附性能，如β分子筛-硅藻土复合材料对苯、甲苯和乙酸乙酯吸附能力分别约为纯β分子筛的4.7~35.3倍。由此可见，这种新型多级多孔分子筛/硅藻土复合材料在吸附分离大分子污染物方面是一种很有前途的吸附材料。然而，由于硅藻土亲水性的表面特性和较差的耐碱性导致在制备复合材料的过程中骨架易被破坏，且制备的复合材料对疏水性和非极性污染物的亲和力差。

1.3　分子筛-活性炭复合材料

活性炭（Activated carbon， AC）是由富碳材料通过炭化、活化处理后得到的一种工程碳基材料，因其比表面积高、孔隙结构发达、表面上含有（或可以附加上）多种官能团、性能稳定（耐酸碱）和易再生等特性，通常被认为是一种几乎“万能”的材料，广泛应用于国防、化工、食品、医药、环保等领域^［80］。由于未经改性的AC表面含有大量的C-C非极性键，具有疏水和亲油的特性，通常其对非极性或极性低的化合物具有较好的吸附效果。此外，AC的孔径分布较广，除含有丰富微孔结构外，还含有少量介孔和大孔。因此，将AC和分子筛组合构建复合材料可以将AC的多孔结构、亲油特性、非极性和分子筛的微孔结构、亲水、极性等特性有机地结合在一起，有望实现同时去除不同种类、不同结构及不同性质混合污染物。

对于分子筛-活性炭复合材料的开发，国内外学者进行了大量研究，其制备方法及结构特征总结见表3。早期是将活性炭、分子筛通过简单地搅拌混合，并加入黏结剂成型制备复合材料。物理混合法简单、易操作，但通过这种方法获得的复合材料经过高温处理后的机械强度较低，容易破碎，无法应用到实际生产中。Narooei等^［81］在物理混合基础上，将其倒入高剪切混合造粒机中进行造粒，虽在一定程度上增强了复合材料的机械强度，但所得复合材料孔隙率降低，材料的颗粒密度相对较高，不利于溶出释放，且该方法能耗较高，所需的生产成本较高。近年来，众多科研工作者利用工业、农副产业废弃物资源（粉煤灰、煤矸石、煤气化残渣或生物质废弃物等）为原料，通过碱浸、炭化、活化和水热处理等工艺，将其中的有机质转化为多孔炭，无机质经水热法合成分子筛，最终制备出分子筛-活性炭复合材料。然而，采用上述方法制备分子筛/活性炭复合材料的过程中涉及炭化、活化、晶化等工序，每个环节受到不同因素影响，因素间相互制约，要实现复合材料结构调控较困难。

Rostami等^［82］以活性炭为基体，将其与硅酸钠溶液混合进行水热反应获得分子筛/活性炭复合材料。该方法具有可控性和可调性，操作简单、快速，成本较低，但由于活性炭表面的疏水性，导致分子筛在活性炭表面覆盖率低且易脱落，没有结合形成具有两者特性的复合材料。Garcı́a等^［83］研究表明：通过物理或化学手段对活性炭表面进行修饰，以调控其疏水性，能在一定程度上提高分子筛在活性炭表面的负载量。然而，该方法仍存在分子筛在活性炭表面沉积不均匀、晶粒间隙较大以及复合材料易开裂等问题，限制了其进一步的性能提升与应用。Vega等^［84］在陈化结束后向硅铝酸盐凝胶中添加活性炭，水热合成分子筛/活性炭复合材料。但由于活性炭优异的吸附性能，合成液主要被活性炭吸附在孔内，堵塞活性炭部分孔道，没有形成具有二者特征的新型材料。目前已报道的活性炭/分子筛复合材料制备方法中都没有合成理想的复合材料，可能是由于活性炭在溶液中表面带负电荷^［85］，其与同样带负电的分子筛晶核间存在静电斥力，阻碍了分子筛晶核在AC表面上的负载，抑制了进一步结晶。因此，对活性炭材料进行表面改性，使其在水溶液中表面电荷发生逆转是解决上述问题的重要途径之一。

1.4　分子筛-聚合物复合材料

分子筛在实验室条件下相对易于合成，但通常以高度分散的粉体形式存在，用于液相或气相吸附时易发生团聚，导致活性中心减少，降低吸附性能。特别是在大规模废水处理中，吸附后的粉状分子筛难以从溶液中分离出来，不利于回收利用。聚合物是具有多种特殊性能的有机化合物，具有比表面积高、机械强度高、化学稳定性好等特性。将分子筛分散并嵌入聚合物网络中，可在很大程度上解决分子筛易团聚问题，增强分子筛与污染物的接触面积，提高其吸附效率。此外，由于分子筛表面带有负电荷，其对溶液中阴离子化合物的亲和力较低。而带正电荷的聚合物对水中的阴离子表现出良好的吸附性能。因此，用各种聚合物改性分子筛表面来合成分子筛/聚合物复合材料被认为是改善分子筛吸附性能及其在吸附过程中易团聚问题的一种有效策略。

迄今为止，研究人员将分子筛与各种天然聚合物（如壳聚糖、海藻酸盐、环糊精等）和合成聚合物（如聚丙烯、聚苯胺等）组合制备了系列分子筛-聚合物复合材料，用于去除各种污染物。目前，分子筛-聚合物复合材料的制备方法主要有溶液共混法、原位聚合法、熔融共混法、溶胶-凝胶法等。溶液共混法是将分子筛和聚合物分别溶解或分散在合适的溶剂中，然后将两种溶液混合并除去溶剂，得到复合材料。这种方法的关键点在于筛选具有良好的溶解性且反应后可彻底移除的溶剂。目前，绝大部分的分子筛-壳聚糖复合材料均通过该方法制备。熔融共混法是分子筛与熔融状态下的聚合物混合，通过机械力使分子筛分散均匀，随后冷却固化成复合材料。该方法具有简便易行、制备效率高、操作性强等特点。原位聚合主要包括分子筛在体系中的分散，以及之后在溶液中引发聚合两个阶段。在这种方法中，分子筛作为模板直接添加到聚合物的单体溶液中，然后引发聚合反应。该方法可以实现分子筛与聚合物的均匀分散，在分子筛表面形成聚合物涂层，增强界面结合，但制备过程易受到温度、pH值和反应时间等因素的影响。溶胶-凝胶法是先制备含分子筛的溶胶，然后引入聚合物前驱体，两者在溶胶阶段混合，随后发生凝胶化，最后固化形成复合材料。该方法可以获得高纯度和高孔隙率的复合材料，但存在反应成本高、反应周期长等缺点。表4总结了分子筛-聚合物复合材料各种制备方法的优缺点。

1.5　其他分子筛基复合材料

除了前述几类分子筛基复合材料被证明能够有效提升单一分子筛的性能外，其他功能性材料（如石墨烯、金属氧化物、层状双氢氧化物等）也被用于分子筛基复合材料的合成，并展现了广阔的应用前景。

1.5.1　分子筛-石墨烯复合材料

石墨烯是一种由碳原子通过sp²杂化形成的蜂窝状单层二维材料，属于碳基材料。氧化石墨烯（GO）是其含氧衍生物，通过氧化石墨剥离制得，表面富含羧基、羟基、环氧基等官能团，使其在水溶液和极性溶剂中稳定存在。这些官能团赋予GO比表面积高、机械强度高、化学稳定性强等优异特性，同时可作为电活性物质的固定位点，促进化学转化^［112］。例如，Kim等^［113］制备的GO/Faujasite复合材料展示出多级孔结构，对亚甲蓝的吸附能力较强（92.4 mg/g），但GO较差的分离能力限制了其实际应用，如果不能完全从受污染的水中分离出来，可能导致二次污染。为了改善GO分离性能差的问题，Shi等^［114］在制备GO和13X复合材料的过程中，添加L-抗坏血酸成功合成了具有多级孔结构的13X分子筛-还原氧化石墨烯（rGO）复合材料。该复合材料在去除水中痕量铅（Ⅱ）方面表现出优异性能，最大吸附容量达到6.07 mg/g，约为13X分子筛（2.72 mg/g）的2.23倍。此外，该复合材料能通过饱和氯化钠溶液进行有效再生，进一步提升了其实际应用潜力。

1.5.2　分子筛-金属氧化物复合材料

金属氧化物，特别是具有磁性（如Fe₂O₃、Fe₃O₄）或半导体特性（如TiO₂、ZnO）的纳米材料也常应用于构建分子筛基复合材料。一方面，金属氧化物的引入能够调控分子筛的表面性质和结构，从而增强其对特定污染物的吸附和催化性能；另一方面，某些金属氧化物的加入也有助于解决分子筛在应用过程中的回收难题。这些复合材料通过吸附或吸附-光催化的协同作用，在污染物去除方面展现了良好的吸附效果^{［115， 116］}。Mesdaghinia等^［117］通过共沉淀法制备了磁性沸石/Fe₃O₄复合材料，所得复合材料对邻苯二甲酸二乙酯的吸附量达到195 mg/g，高于纯沸石的71 mg/g；Suazo等^［118］制备的Fe⁰-沸石复合材料对水中As（V）吸附量高达47.30 mg/g，是纯沸石吸附量（1.78 mg/g）的25倍。

1.5.3　分子筛-层状双氢氧化物复合材料

层状双氢氧化物（LDHs）是一类二维纳米结构材料，由带正电的金属氢氧化物层与带负电的阴离子层交替堆叠形成^［119］。LDHs具有独特的性质，如组成和结构的可调控性、阴离子交换性、生物相容性和无毒性，广泛应用于阴离子交换、药物输送、催化反应及废水处理等领域^［120］。由于这些优异特性，研究人员将LDHs引入分子筛框架中，以增强分子筛的多功能性。分子筛-LDHs复合材料通过将LDHs的阴离子和疏水框架特性与沸石分子筛的阳离子和亲水层特性协同结合，广泛应用于环境修复、药物传递、气体吸附与分离、能源存储和催化等领域。目前已开发出多种此类复合材料，如Y@LDH、 ZSM-5@LDH、TS-1@LDH^［121］、Faujasite-Na zeolite/LDHs和NaP-zeolite/LDHs^［122］等。

1.6　分子筛基复合材料制备方法比较

基于应用场景的变化，分子筛基复合材料的复合模式多种多样，不同复合模式发展了众多合成方法。目前，分子筛基复合材料常用的制备方法的过程、结构特征及优缺点的总结如表5所示。

经模板法、附晶生长法、溶胶-凝胶法和分子筛硅源法等方法将同种或不同种类的多元分子筛组装在同一个材料颗粒中，构建具有梯度酸分布和孔分布的复合分子筛，能实现各种分子筛间的协同效应，弥补单种分子筛的局限性。但目前国内外对复合分子筛的合成研究还仅仅处于起步阶段，不同种类分子筛在结构上存在相互制约的问题，得到的复合分子筛结构不稳定，易发生相分离。分子筛与其他材料组合构建的复合材料能够充分发挥两者的优势并消除各自的缺点，通过这些方法一般只能制备粉体复合材料，关于分子筛与客体材料的结合过程和晶体生长过程影响因素的控制等方面缺乏深入研究，还没有得出令人满意的结论。在分子筛与其他材料组合过程中，静电自组装方法和溶液共混法相较其他合成方法有明显的优势。静电自组装法基于电荷间的相互作用，能促使分子筛颗粒与带相反电荷的客体材料自动聚集，形成有序的结构，通过调整材料的电荷性质和浓度，可以控制复合材料的形貌、尺寸和内部结构，从而指导具有不同功能的分子筛基复合材料的制备。静电自组装法也存在一定的弊端：过程可能受到pH值、温度、离子强度等因素的影响，这些都可能导致组装失败或效果不佳，需要进一步探究。溶液共混法适合分子筛与多数材料的组合，但其对溶剂的依赖性比较强，可能使制备出来的复合材料实际生成样品与预期结果存在差别。

2 分子筛基复合材料的应用

通过用不同的合成方法和不同的基体材料开发了一系列具有多功能的分子筛基复合材料，显著改善了单种分子筛的物理化学性质，如多级孔隙结构、双重酸性位点、亲/疏水性、极性/非极性表面特性等，扩宽了其应用领域。为了更好地比较不同类型的分子筛基复合材料，表6总结了分子筛基复合材料的典型应用。

2.1　吸附材料

分子筛基复合材料最重要的应用领域是吸附分离，既用于液相吸附，如重金属离子、染料、抗生素和芳香族化合物等，也用于气相吸附，包括VOCs吸附净化、CO₂捕集、CH₄/N₂吸附分离、H₂S吸附等^［128］。与传统微孔分子筛相比，分子筛基复合材料具有更好的物理化学稳定性和更强的吸附能力，更易重复使用。

Li等^［129］采用后处理法制备了ZSM-5/MCM-41和ZSM-5/Silicalite-1复合材料用于潮湿条件下对甲苯的吸附净化。在相对湿度50%条件下，ZSM-5/MCM-41和ZSM-5/Silicalite-1对甲苯的穿透时间分别是纯ZSM-5的1.6倍和1.2倍。Li等^［89］报道了分子筛-活性炭复合材料在水溶液中吸附罗丹明B的应用。复合材料展现出多级孔结构，其对罗丹明B的去除率达到94.2%，高于纯分子筛（17.0%）。Li等^［130］通过原位合成法制备的ZSM-5/SBA-15复合分子筛对甲苯的穿透时间比ZSM-5长近4.6倍，呈现更为优异的甲苯吸附性能，这归因于晶内介孔不仅提高了吸附剂的比表面积，还缩短了甲苯的扩散途径，从而提高了吸附效率。

2.2　催化材料

分子筛基复合材料的另一个重要应用领域是工业催化，其在催化裂化、加氢裂化、催化重整、芳烃和烷烃异构化、烯烃聚合和烷基化等方面表现出优异的催化性能^{［131， 132］}。

Tang等^［18］通过纳米自组装法制备了ZSM-5/MCM-41复合分子筛，用于催化甲醇脱水生成二甲醚。在170~290 °C的反应温度下，与纯ZSM-5分子筛相比（活性为86.7%，选择性从98%迅速下降至86%；在甲醇转化率约为85%时，活性可维持15 d，但30 d后下降至45%），ZSM-5/MCM-41（经1.5 mol/L碱处理）表现出更高的甲醇脱水活性（86.6%）、选择性（100%）和稳定性（在30 d内甲醇转化率保持在85%以上）。这种优异性能归因于复合材料有效结合了介孔分子筛的通道优势与微孔分子筛的酸性特性。刘鹏等^［133］通过后合成法制备了一系列不同硅铝比的ZSM-5-SBA-15复合分子筛，其既有SBA-15介孔结构，又有ZSM-5型分子筛的微孔结构。在甲苯甲醇烷基化制备对二甲苯的反应中，系列ZSM-5-SBA-15复合分子筛在400 ℃时的选择性是纯ZSM-5的两倍多。这归因于SBA-15部分覆盖了ZSM-5外表面的酸性位点，从而抑制了对二甲苯在外表面发生的二级异构化反应。

3 结 论

（1）分子筛基复合材料基本可归为两类：同种或不同种类的多元分子筛组装在同一个材料颗粒中，形成具有梯度酸分布和孔分布的复合分子筛；分子筛与具有特定功能的客体材料组合构建的分子筛基复合材料。

（2）模板法、附晶生长法、溶胶-凝胶法和分子筛硅源法等方法是制备复合分子筛的常用有效手段。但由于缺乏合成化学、复合机理及结构方面的深入研究与探讨，导致复合分子筛的设计与制备主要依赖经验，通过这些方法得到的复合分子筛结构不稳定，易发生相分离。未来可在这些方面继续探索，以提高分子筛间的结合强度。

（3）分子筛与其他客体材料的组合可以通过多种途径来构建。溶液共混法简单方便、易操作控制，但该方法对溶剂依赖性强，在材料结合强度和孔结构的可控性方面存在不足，难以获得孔结构高度发达且结构稳定的复合材料。静电自组装方法虽然有助于保持分子筛的结构完整性，可以在多种类型的基底上进行自组装，获得具有不同功能特性的分子筛基复合材料，但合成过程复杂、成本较高等问题也限制了它的大规模应用。

（4）分子筛基复合材料在环境吸附与催化领域有着广阔的应用前景。尽管其在液相有机污染物吸附及多相催化方面已取得显著进展，但针对气相有机污染物，尤其是VOCs的研究相对较少，未来可以在这个方面继续开展相关研究探索。

（5）未来研究应更加注重温和条件下的合成策略，尤其是在低温低压环境中开发复合材料。这不仅有助于降低成本和能耗，还能提升复合材料的结构稳定性。此外，使用环保型溶剂体系将有助于减小环境影响，进一步提高工艺的可持续性。

参考文献

[1] Busca G. Acidity and basicity of zeolites: a fundamental approach[J]. Microporous and Mesoporous Materials, 2017, 254: 3-16.

[2] Li Y, Li L, Yu J. Applications of zeolites in sustainable chemistry[J]. Chem, 2017, 3(6): 928-949.

[3] Xu H, Zhu L, Wu Q, et al. Advances in the synthesis and application of the SSZ-39 zeolite[J]. Inorganic Chemistry Frontiers, 2022, 9(6): 147-157.

[4] Möller K, Bein T. Mesoporosity-a new dimension for zeolites[J]. Chemical Society reviews, 2013, 42(9): 3689-3707.

[5] Frising T, Leflaive P. Extraframework cation distributions in X and Y faujasite zeolites: a review[J]. Microporous and Mesoporous Materials, 2008, 114(1-3): 27-63.

[6] Roshanfekr R L, Anbia M. Zeolite-based composites for the adsorption of toxic matters from water: a review[J]. Journal of Environmental Chemical Engineering, 2021, 9(5): 106088.

[7] 王迎运, 周亚松, 魏强, 等. Y/β复合分子筛制备方法及应用研究进展[J]. 化工进展, 2016, 35(): 155-159.

[8] Wang Ying-song, Zhou Ya-song, Wei Qiang, et al. Advances in synthesis and applications of Y/B core-shell composite molecular sieves[J]. Chemical Industry and Engineering Progress, 2016, 35(Sup.2): 155-159.

[9] Foo K Y, Hameed B H. The environmental applications of activated carbon/zeolite composite materials[J]. Advances in Colloid and Interface Science, 2011, 162(1/2): 22-28.

[10] Tanyol M, Kavak N, Torğut G. Synthesis of poly (AN-co-VP)/zeolite composite and its application for the removal of brilliant green by adsorption process: kinetics, isotherms, and experimental design[J]. Advances in Polymer Technology, 2019, 2019: 1-12.

[11] Dai S, Zhang L, Hao C, et al. Preparation and characterization of zeolite/diatomite composite materials[J]. Materials Research Express, 2019, 6(12): 125516.

[12] Ivanova I I, Knyazeva E E. Micro-mesoporous materials obtained by zeolite recrystallization: synthesis, characterization and catalytic applications[J]. Chemical Society Reviews, 2013, 42(9): 3671-3688.

[13] Masoumifard N, Guillet N R, Kleitz F. Synthesis of engineered zeolitic materials: from classical zeolites to hierarchical core-shell materials[J]. Advanced Materials, 2018, 30(16): 1704439.

[14] Kokotailo G T, Woodbury N J. Crystalline zeolite product constituting ZSM-5/ZSM-11 intermediates [P]. United States Patent: 4229424, 1980-10-21.

[15] Chen H, Shen B, Pan H. In situ formation of ZSM-5 in NaY gel and characterization of ZSM-5/Y composite zeolite[J]. Chemistry Letters, 2003, 32(8): 726-727.

[16] Ghrib Y, Frini S N, Srasra E, et al. Synthesis of cocrystallized USY/ZSM-5 zeolites from kaolin and its use as fluid catalytic cracking catalysts[J]. Catalysis Science & Technology, 2018, 8(3): 716-725.

[17] Pan M, Li P, Zheng J, et al. Zeolite-zeolite composite composed of Y zeolite and single-crystal-like ZSM-5 zeolite: fabricated by a process like "big fish swallowing little one"[J]. Materials Chemistry and Physics, 2017, 194: 49-54.

[18] Sang Y, Liu H, He S, et al. Catalytic performance of hierarchical H-ZSM-5/MCM-41 for methanol dehydration to dimethyl ether[J]. Journal of Energy Chemistry, 2013, 22(5): 769-777.

[19] Tang Q, Xu H, Zheng Y, et al. Catalytic dehydration of methanol to dimethyl ether over micro–mesoporous ZSM-5/MCM-41 composite molecular sieves[J]. Applied Catalysis A: General, 2012, 41: 36-42.

[20] Xiong G, Meng F, Liu J, et al. Rapid hydrothermal synthesis of hierarchical ZSM-5/beta composite zeolites[J]. RSC Advances, 2021, 11(35): 21235-21247.

[21] Chen X, Jiang R, Hou H, et al. Synthesis of ZSM-5/SAPO-34 zeolite composites from LAPONITE® and their catalytic properties in the MTO reaction[J]. CrystEngComm, 2020, 22(37): 6182-6188.

[22] Wang X X, Guo S L, Niu Z Y. Synthesis of a ZSM-5 (core)/SAPO-11 (shell) composite zeolite and its catalytic performance in the methylation of naphthalene with methanol[J]. RSC Advances, 2023, 13:No. 2081.

[23] Dzikh I P, Lopes J M, Lemos F, et al. Temperature dependence of the USHY+HZSM-5 mixing effect on the n-heptane transformation[J]. Catalysis Today, 2001, 65(2): 143-148.

[24] 张球, 谭薇, 郑家军, 等. 气相转移法制备多孔双相沸石复合物[J]. 无机材料学报, 2014, 29(9): 985-990.

[25] Zhang Qiu, Tan Wei, Zheng Jia-jun, et al. Hierachical zeolite-zeolite composite prepared by a vapor phase transport method[J]. Journal of Inorganic Materials, 2014, 29(9): 985-990.

[26] 时启涛,孙万付,张志智,等. MOR/EU-1复合分子筛的合成与表征[J]. 当代化工,2011,40(3): 260-264.

[27] Shi Qi-tao, Sun Wan-fu, Zhang Zhi-zhi, et al. Synthesis and characterization of MOR/EU-1 composite molecular sieves[J]. Contemporary Chemical Industry, 2011, 40(3): 260-264.

[28] Huang L, Guo W, Deng P, et al. Investigation of synthesizing MCM-41/ZSM-5 composites[J]. The Journal of Physical Chemistry B, 2000, 104(13): 2817-2823.

[29] Huyen P T, Nam L T H, Vinh T Q, et al. ZSM-5/SBA-15 versus Al-SBA-15 as supports for the hydrocracking/hydroisomerization of alkanes[J]. Catalysis Today, 2018, 306: 121-127.

[30] Kloetstra K R, Zandbergen H W, Jansen J C, et al. Overgrowth of mesoporous MCM-41 on faujasite[J]. Microporous Materials, 1996, 6(5/6): 287-293.

[31] Shan W, Tao D, Li Y P. Synthesis of a new meso/ microporous composite molecular sieve of MCM-41/ mordenite[J]. Science Bulletin, 2005, 50(12): 1180-1184.

[32] Wang Y, Cui D, Li Q. Synthesis, characterization and influence parameters on the overgrowth of micro/mesoporous Y-zeolite-MCM-41 composite material under acidic conditions[J]. Microporous and Mesoporous Materials, 2011, 142(2/3): 503-510.

[33] 30] Prokešová P, Mintova S, Ejka J, et al. Preparation of nanosized micro/mesoporous composites via simultaneous synthesis of Beta/MCM-48 phases[J]. Microporous and Mesoporous Materials, 2003, 64(1-3): 165-174.

[34] 马燕辉, 赵会玲, 唐圣杰, 等. 微孔/介孔复合分子筛的合成及其对CO₂的吸附性能[J]. 物理化学学报, 2011, 27(3): 689-696.

[35] Ma Yan-hui, Zhao Hui-ling, Tang Sheng-jie, et al. Synthesis of Micro/Mesoporous composites and their application as CO₂ adsorbents[J]. Acta Physico-Chimica Sinica, 2011, 27(3): 689-696.

[36] Yang G, Yang J, Huang D, et al. BTX production from rice husk by fast catalytic pyrolysis over a Ga-modified ZSM-5/SBA-15 catalyst[J]. New Journal of Chemistry, 2021, 45(8): 3809-3816.

[37] Prokešová P, Mintova S, Cejka J, et al. Preparation of nanosized micro/mesoporous composites via simultaneous synthesis of Beta/MCM-48 phases[J]. Microporous and Mesoporous Materials, 2003, 64: 165-174.

[38] Jokar F, Alavi S M, Rezaei M. Investigating the hydroisomerization of n-pentane using Pt supported on ZSM-5, desilicated ZSM-5, and modified ZSM-5/MCM-41[J]. Fuel, 2022, 324: 124511.

[39] Xia Y, Mokaya R. On the synthesis and characterization of ZSM-5/MCM-48 aluminosilicate composite materials[J]. Journal of Materials Chemistry, 2004, 14(5): 863-870.

[40] Xiong G, Zhou S, Liu L, et al. Aerosol assisted synthesis of Y/ZSM‐5 composite zeolite and its application in cracking reaction[J]. European Journal of Inorganic Chemistry, 2022(24): 1-9.

[41] Lv Y, Wang X, Gao D, et al. Hierarchically porous ZSM-5/SBA-15 zeolite: tuning pore structure and acidity for enhanced hydro-upgrading of FCC gasoline[J]. Industrial & Engineering Chemistry Research, 2018, 57(42): 14031-14043.

[42] 刘佳, 张士明, 宋兆阳, 等. 加氢裂化复合分子筛催化剂研究进展[J]. 当代化工, 2024, 53(3): 664-671.

[43] Liu Jia, Zhang Shi-ming, Song Zhao-yang, et al. Research progress of composite molecular sieve catalysts in hydrocracking[J]. Contemporary Chemical Industry, 2024, 53(3): 664-671.

[44] Wang W, He L, Luo Q, et al. Synthesis and application of core-shell, hollow, yolk-shell multifunctional structure zeolites[J]. Microporous and Mesoporous Materials, 2023, 362: 112766.

[45] Rollmann L D. ZSM-5 containing aluminum-free shells on its surface[P]. United States Patent: 4088605, 1978-05-09.

[46] Chu P, Schwartz A B. Zeolite catalyst composition and synthesis method[P]. United States Patent: 4868146, 1989-09-19.

[47] Li Q, Wang Z, Hedlund J, et al. Synthesis and characterization of colloidal zoned MFI crystals[J]. Microporous and Mesoporous Materials, 2005, 78(1): 1-10.

[48] Okamoto M, Huang L, Yamano M, et al. Skeletal isomerization of tetradecane catalyzed by TON-type zeolites with a fragmented core-shell structure[J]. Applied Catalysis A: General, 2013, 455: 122-128.

[49] Miyamoto M, Iwatsuka H, Oumi Y, et al. Effect of core-shell structuring of chabazite zeolite with a siliceous zeolite thin layer on the separation of acetone-butanol-ethanol vapor in humid vapor conditions[J]. Chemical Engineering Journal, 2019, 363: 292-299.

[50] Wang S, Bai P, Wei Y, et al. Three-dimensional-printed core-shell structured MFI-Type zeolite monoliths for volatile organic compound capture under humid conditions[J]. ACS Applied Materials & Interfaces, 2019, 11(42): 38955-38963.

[51] Bing L, Li F, Li Q, et al. One-pot synthesis of core-shell structured SSZ-13 zeolite using aluminum isopropoxide as an aluminum source[J]. Materials Letters, 2020, 266: 127497.

[52] Zhang B Z, Liu X P. Catalytic performance of MFI/MFI core-shell zeolites in benzene methylation[J]. China Petroleum Processing and Petrochemical Technology, 2014, 16(4): 94-99.

[53] Jin Z H, Liu S, Qin L, et al. Methane dehydroaromatization by Mo-supported MFI-type zeolite with core–shell structure[J]. Applied Catalysis A: General, 2013, 453: 295-301.

[54] Wang Q H, Wang X C, Dai W J, et al. Core-shell SAPO-34@ZSM-5 composite via in situ solid-solid transformation of pre-coating MCM-41 shell and its application in methanol-to-olefins[J]. Microporous and Mesoporous Materials, 2023, 353: No.112498.

[55] Advani J H, Manal A K, Kanna N, et al. Synthesis of core-shell structured zeolite nanocomposite comprising ZSM-5 core and zeolite Y shell[J]. Materials Letters, 2024, 360: 135994.

[56] 王英杰, 李博文, 何佳丽, 等. 核壳型介微孔复合分子筛MCM-41@TS-1的合成及其催化性能[J]. 硅酸盐学报, 2022, 50(10): 2611-2621.

[57] Wang Ying-jie, Li Bo-wen, He Jia-li, et al. Synthesis and catalytic performance of core-shell micro-mesoporous composite zeolite MCM-41@TS-1 catalysts[J]. Journal of the Chinese Ceramic Society, 2022, 50(10): 2611-2621.

[58] 亢玉红, 马亚军, 李健. ZSM5/Y 核-壳复合分子筛的合成、表征及其催化性能研究[J]. 现代化工,2016, 36(10): 76-79.

[59] Kang Yu-hong, Ma Ya-jun, Li Jian. Synthesis, characterization and catalytic property of ore-shell MFI-FAU-Zeolite composite molecular sieve[J]. Modern Chemical Industry, 2016, 36(10): 76-79.

[60] Yu L, Farinmade A, Ajumobi O, et al. MCM-41/ZSM-5 composite particles for the catalytic fast pyrolysis of biomass[J]. Applied Catalysis A: General, 2020, 602: 117727.

[61] Zheng J, Zhang X, Wang Y, et al. Synthesis and catalytic performance of a bi-phase core-shell zeolite composite[J]. Journal of Porous Materials, 2009, 16(6): 731-736.

[62] Li X, Rezaei F, Ludlow D K, et al. Synthesis of SAPO-34@ZSM-5 and SAPO-34@Silicalite-1 core-shell zeolite composites for ethanol dehydration[J]. Industrial & Engineering Chemistry Research, 2018, 57(5): 1446-1453.

[63] Qian X F, Li B, Hu Y Y, et al. Exploring meso‐/microporous composite molecular sieves with core-shell structures[J]. Chemistry-A European Journal, 2012, 18(3): 931-939.

[64] Qian X, Du J, Li B, et al. Controllable fabrication of uniform core-shell structured zeolite@SBA-15 composites[J]. Chemical Science, 2011, 2(10): 2006-2016.

[65] 纪永军, 张斌, 张坤, 等. ZSM-5@Mesoporous Silica 核壳复合结构分子筛的制备及其甲苯甲醇烷基化择形催化性能的研究[J]. 化学学报,2013,71: 371-380.

[66] Ji Yong-jun, Zhang Bin, Zhang Kun, et al. Core/shell-structured ZSM-5@Mesoporous silica composites for shape-selective alkylation of toluene with methanol[J]. Acta Chimica Sinica, 2013, 71: 371-380.

[67] Li Q, Wen Z, Zhang Z, et al. Surfactant-assisted hydrothermal synthesis of core-shell ZSM-5@SSZ-13 zeolite for methanol to olefins reaction[J]. Molecular Catalysis, 2023, 547: 113321.

[68] Yu H, Lv Y, Ma K, et al. Synthesis of core-shell structured zeolite-A@mesoporous silica composites for butyraldehyde adsorption[J]. Journal of Colloid and Interface Science, 2014, 428: 251-256.

[69] Liu L, Singh R, Li G, et al. Synthesis of hydrophobic zeolite X@SiO₂ core-shell composites[J]. Materials Chemistry and Physics, 2012, 133(2/3): 1144-1151.

[70] Ye X, Kang S, Wang H, et al. Modified natural diatomite and its enhanced immobilization of lead, copper and cadmium in simulated contaminated soils[J]. Journal of Hazardous Materials, 2015, 289: 210-218.

[71] Garderen N V, Clemens F J, Kaufmann J, et al. Pore analyses of highly porous diatomite and clay based materials for fluidized bed reactors[J]. Microporous and Mesoporous Materials, 2012, 151: 255-263.

[72] Liu H, Lu G, Guo Y, et al. Effect of pretreatment on properties of TS-1/diatomite catalyst for hydroxylation of phenol by H₂O₂ in fixed-bed reactor[J]. Catalysis Today, 2004, 93: 353-357.

[73] Liu H, Lu G, Guo Y, et al. Deactivation and regeneration of TS-1/diatomite catalyst for hydroxylation of phenol in fixed-bed reactor[J]. Chemical Engineering Journal, 2005, 108(3): 187-192.

[74] Liu H, Lu G, Guo Y, et al. Chemical kinetics of hydroxylation of phenol catalyzed by TS-1/diatomite in fixed-bed reactor[J]. Chemical Engineering Journal, 2006, 116(3): 179-186.

[75] Liu X, Yang C, Wang Y, et al. Effect of the diatomite pretreatment on the catalytic performance of TS-1/diatomite for toluene hydroxylation by H₂O₂ in fixed-bed reactor[J]. Chemical Engineering Journal, 2014, 243: 192-196.

[76] Anderson M W, Holmes S M, Hanif N, et al. Hierarchical pore structures through diatom zeolitization[J]. Angewandte Chemie International Edition, 2000, 39(15): 2707-2710.

[77] Jia Y, Han W, Xiong G, et al. A method for diatomite zeolitization through steam-assisted crystallization with in-situ seeding[J]. Materials Letters, 2008, 62(16): 2400-2403.

[78] Peng H, Xu L, Wu H, et al. Synthesis and formation mechanism of TS-1@mesosilica core-shell materials templated by triblock copolymer surfactant[J]. Microporous and Mesoporous Materials, 2012, 153: 8-17.

[79] Al-Ghouti M A, Khraisheh M A M, Ahmad M N M, et al. Adsorption behaviour of methylene blue onto Jordanian diatomite: a kinetic study[J]. Journal of Hazardous Materials, 2009, 165(1-3): 589-598.

[80] Wang Y J, Tang Y, Wang X D, et al. Fabrication of hierarchically structured zeolites through layer-by-layer assembly of zeolite nanocrystals on diatom templates[J]. Chemistry Letters, 2001, 30(11): 1118-1119.

[81] Wang Y, Tang Y, Dong A, et al. Zeolitization of diatomite to prepare hierarchical porous zeolite materials through a vapor-phase transport process[J]. Journal of Materials Chemistry, 2002, 12(6): 1812-1818.

[82] Yuan W, Yuan P, Liu D, et al. A hierarchically porous diatomite/silicalite-1 composite for benzene adsorption/desorption fabricated via a facile pre-modification in situ synthesis route[J]. Chemical Engineering Journal, 2016, 294: 333-342.

[83] Yuan W, Yuan P, Liu D, et al. Novel hierarchically porous nanocomposites of diatomite-based ceramic monoliths coated with silicalite-1 nanoparticles for benzene adsorption[J]. Microporous and Mesoporous Materials, 2015, 206: 184-193.

[84] Yuan W, Yuan P, Liu D, et al. In situ hydrothermal synthesis of a novel hierarchically porous TS-1/modified-diatomite composite for methylene blue (MB) removal by the synergistic effect of adsorption and photocatalysis[J]. Journal of Colloid and Interface Science, 2016, 462: 191-199.

[85] Yu W, Yuan P, Liu D, et al. Facile preparation of hierarchically porous diatomite/MFI-type zeolite composites and their performance of benzene adsorption: the effects of NaOH etching pretreatment[J]. Journal of Hazardous Materials, 2015, 285: 173-181.

[86] Yu W, Deng L, Yuan P, et al. Preparation of hierarchically porous diatomite/MFI-type zeolite composites and their performance for benzene adsorption: the effects of desilication[J]. Chemical Engineering Journal, 2015, 270: 450-458.

[87] Yu S Y, Wang X Y, Liu F, et al. Adsorption of acetone, ethyl acetate and toluene by beta zeolite/diatomite composites: preparation, characterization and adsorbability[J]. Environmental Science and Pollution Research, 2022, 29(53): 80646-80656.

[88] 解强, 张香兰, 梁鼎成,等. 煤基活性炭定向制备:原理·方法·应用[J]. 煤炭科学技术, 2021, 49(1): 100-127.

[89] Xie Qiang, Zhang Xiang-lan, Liang Ding-cheng, et al. Directional preparation of coal-based activated carbonprinciples,approaches and applications[J]. Coal Science and Technology, 2021, 49(1): 100-127.

[90] Narooei E, Mohebbi K D, Samimi A, et al. Preparation and characteristics' evaluation of zeolite/activated carbon composite granules, using high shear mixer granulator[J]. Materials Research Express, 2019, 6(12): 125532.

[91] Rostami M, Mofarahi M, Karimzadeh R, et al. Preparation and characterization of activated carbon–zeolite composite for gas adsorption separation of CO2/N2 system[J]. Journal of Chemical & Engineering Data, 2016, 61(7): 2638-2646.

[92] Garcı́a M J, Cazorla A D, Linares S A, et al. Synthesis and characterisation of MFI-type zeolites supported on carbon materials[J]. Microporous and Mesoporous Materials, 2001, 42(2): 255-268.

[93] Vega S D R, Muñoz S J C, Borrero N J, et al. Removal of linear siloxanes and dimethyl sulfone from water using hierarchical zeolite porous carbon adsorbents[J]. Journal of Hazardous Materials, 2022, 440:129805.

[94] Yuan C, Huang Y, Cannon F S, et al. Adsorption mechanisms of PFOA onto activated carbon anchored with quaternary ammonium/epoxide-forming compounds: a combination of experiment and model studies[J]. Journal of Environmental Sciences, 2020, 98: 94-102.

[95] Halim A A, Aziz H A, Johari M A M. Removal of ammoniacal nitrogen and COD from semi-aerobic landfill leachate using low-cost activated carbon-zeolite composite adsorbent[J]. International Journal of Environment & Waste Management, 2009, 4(3):399-411.

[96] Lim C K, Bay H H, Neoh C H, et al. Application of zeolite-activated carbon macrocomposite for the adsorption of Acid Orange 7: isotherm, kinetic and thermodynamic studies[J]. Environmental Science & Pollution Research, 2013, 20(10): 7243-7255.

[97] Seyedein G S M R, Lotfollahi M N. Preparation of granular composite materials as novel sorbents and their application for removal of heavy metals from solution[J]. International Journal of Environmental Science and Technology, 2019, 16(7): 3697-3706.

[98] Li H, Zheng F, Wang J, et al. Facile preparation of zeolite-activated carbon composite from coal gangue with enhanced adsorption performance[J]. Chemical Engineering Journal, 2020, 390: 124513.

[99] Zhang Y, Yu F, Cheng W, et al. Adsorption equilibrium and kinetics of the removal of ammoniacal nitrogen by zeolite x/activated carbon composite synthesized from elutrilithe[J]. Journal of Chemistry, 2017, 2017: 1-9.

[100] Bu N J, Wu J, Zhen Q. Application of the synthesized activated carbon-4A zeolite composite from elutrilithe in wastewater treatment[J]. Journal of Nanoscience and Nanotechnology, 2017, 17(1): 766-772.

[101] Xue C L, Cheng W P, Hao W M, et al. CH₄/N₂ adsorptive separation on zeolite X/AC composites[J]. Journal of Chemistry, 2019, 2019: 1-9.

[102] Ma J, Si C, Li Y, et al. CO₂ adsorption on zeolite X/activated carbon composites[J]. Adsorption, 2012, 18(5): 503-510.

[103] Cheng W P, Gao W, Cui X, et al. Phenol adsorption equilibrium and kinetics on zeolite X/activated carbon composite[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 62: 192-198.

[104] Gao N F, Kume S, Watari K. Zeolite-carbon composites prepared from industrial wastes: (I) effects of processing parameters[J]. Materials Science and Engineering: A, 2005, 399(1): 216-221.

[105] Gao N F, Kume S, Watari K. Zeolite-carbon composites prepared from industrial wastes: (Ⅱ) evaluation of the adaptability as environmental materials[J]. Materials Science and Engineering A, 2005, 404(1/2): 274-280.

[106] Zhao M, Ma X, Chen D, et al. Preparation of honeycomb-structured activated carbon-zeolite composites from modified fly ash and the adsorptive removal of Pb(Ⅱ)[J]. ACS Omega, 2022, 7(11): 9684-9689.

[107] Jha V K, Matsuda M, Miyake M. Sorption properties of the activated carbon-zeolite composite prepared from coal fly ash for Ni²⁺, Cu²⁺, Cd²⁺ and Pb²⁺ [J]. Journal of Hazardous Materials, 2008, 160(1): 148-153.

[108] Isaac P J, Amaravadi S. Synthesis of zeolite/activated carbon composite material for the removal of Lead (Ⅱ) and Cadmium (Ⅱ) ions[J]. Environmental Progress & Sustainable Energy, 2019, 38(6): 1-12.

[109] Purnomo C W. Utilization of bagasse fly ash for carbon-zeolite composite preparation[J]. Journal of Porous Materials, 2013, 20(5): 1305-1313.

[110] Wongcharee S, Aravinthan V, Erdei L. Mesoporous activated carbon-zeolite composite prepared from waste macadamia nut shell and synthetic faujasite[J]. Chinese Journal of Chemical Engineering, 2019, 27(1): 226-236.

[111] Wang M, Xie R, Chen Y, et al. A novel mesoporous zeolite-activated carbon composite as an effective adsorbent for removal of ammonia-nitrogen and methylene blue from aqueous solution[J]. Bioresource Technology, 2018, 268: 726-732.

[112] Khanday W A, Marrakchi F, Asif M, et al. Mesoporous zeolite-activated carbon composite from oil palm ash as an effective adsorbent for methylene blue[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 70: 32-41.

[113] Ngah W S W, Teong L C, Toh R H, et al. Utilization of chitosan-zeolite composite in the removal of Cu(Ⅱ) from aqueous solution: adsorption, desorption and fixed bed column studies[J]. Chemical Engineering Journal, 2012, 209: 46-53.

[114] Ngah W S W, Teong L C, Wong C S, et al. Preparation and characterization of chitosan-zeolite composites[J]. Journal of Applied Polymer Science, 2012, 125: 2417-2425.

[115] Arcibar O J A, Flores R A I, Rangel M J R, et al. Synergistic effect of zeolite/chitosan in the removal of fluoride from aqueous solution[J]. Environmental Technology, 2020, 41(12): 1554-1567.

[116] Kaygun A, Akyil S. Study of the behaviour of thorium adsorption on PAN/zeolite composite adsorbent[J]. Journal of Hazardous Materials, 2007, 147(1/2): 357-362.

[117] Shyaa A A, Hasan O A, Abbas A M. Synthesis and characterization of polyaniline/zeolite nanocomposite for the removal of Chromium(Ⅵ) from aqueous solution[J]. Journal of Saudi Chemical Society, 2015, 19(1): 101-107.

[118] Simsek S, Ulusoy U. UO₂ ²⁺, T^l+, Pb²⁺, Ra²⁺, Bi³⁺ and Ac³⁺ adsorption onto polyacrylamide-zeolite composite and its modified composition by phytic acid[J]. Journal of Radioanalytical and Nuclear Chemistry, 2004,261(1): 79-86.

[119] Motsa M M, Mamba B B, Thwala J M, et al. Preparation, characterization, and application of polypropylene-clinoptilolite composites for the selective adsorption of lead from aqueous media[J]. Journal of Colloid and Interface Science, 2011, 359(1): 210-219.

[120] Lin J, Zhan Y. Adsorption of humic acid from aqueous solution onto unmodified and surfactant-modified chitosan/zeolite composites[J]. Chemical Engineering Journal, 2012, 200: 202-213.

[121] Subramanian N, Perumal T, Mangesh V L, et al. Future perspectives on zeolite/graphene oxide composite synthesis and applications[J]. Energy & Fuels, 2023, 37(22): 17013-17051.

[122] Kim J, Lee C, Kim W, et al. Adsorption equilibria of water vapor on alumina, zeolite 13X, and a zeolite X/activated carbon composite[J]. Journal of Chemical & Engineering Data, 2003, 48(1): 137-141.

[123] Shi Y, Ren X, Zheng H, et al. Hierarchical 13X zeolite/reduced graphene oxide porous material for trace Pb (II) capturing from drinking water[J]. Microporous and Mesoporous Materials, 2022, 329: 111540.

[124] Li Z, Wang L, Meng J, et al. Zeolite-supported nanoscale zero-valent iron: new findings on simultaneous adsorption of Cd(Ⅱ), Pb(Ⅱ), and As(Ⅲ) in aqueous solution and soil[J]. Journal of Hazardous Materials, 2018, 344: 1-11.

[125] Costa M Y, De Andrade M B, Ellena J, et al. Zeolite/ZnO composites based on a Cuban natural clinoptilolite and preliminary evaluation in methylene blue adsorption[J]. Materials Research Express, 2020, 7(1):1-9.

[126] Mesdaghinia A, Azari A, Nodehi R N, et al. Removal of phthalate esters (PAEs) by zeolite/Fe₃O₄: investigation on the magnetic adsorption separation, catalytic degradation and toxicity bioassay[J]. Journal of Molecular Liquids, 2017, 233: 378-390.

[127] Suazo H J, Sepúlveda P, Manquián C K, et al. Synthesis and characterization of zeolite-based composites functionalized with nanoscale zero-valent iron for removing arsenic in the presence of selenium from water[J]. Journal of Hazardous Materials, 2019, 373: 810-819.

[128] Ivanova I I, Knyazeva E E. Micro-mesoporous materials obtained by zeolite recrystallization: synthesis, characterization and catalytic applications[J]. Chemical Society Reviews, 2013, 42(9): 3671-3688.

[129] Prokešová P, Ilková N, Mintova S, et al. Catalytic activity of micro/mesoporous composites in toluene alkylation with propylene[J]. Applied Catalysis A: General, 2005, 281(1/2): 85-91.

[130] Li R, Xue T, Bingre R, et al. Microporous zeolite@vertically aigned Mg-Al layered double hydroxide core@shell structures with improved hydrophobicity and toluene adsorption capacity under wet conditions[J]. ACS Applied Materials & Interfaces, 2018, 10(41): 34834-34839.

[131] Xie X, Xu L, Pan Y, et al. Facile synthesis of rose-like composites of zeolites and layered double hydroxides: growth mechanism and enhanced properties[J]. Chemosphere, 2022, 309: 136741.

[132] 齐硕, 王家亮, 张红丹, 等. 软模板法制备多级孔沸石分子筛的研究进展[J]. 中国科学:化学, 2024, 54(6): 822-836.

[133] Qi Shuo, Wang Jia-liang, Zhang Hong-dan, et al. Advances in preparation of hierarchical zeolites via soft template method[J]. Scientia Sinica Chimica, 2024, 54(6): 822-836.

[134] 于文宇, 阮艳军, 秦玉才, 等. HY/MCM-41分子筛的制备及改性后在吸附脱硫中的应用[J]. 石油化工高等学校学报, 2014, 27(3): 41-47.

[135] Yu Wen-yu, Ruan Yan-jun, Qin Yu-cai, et al. Preparation of HY/MCM-41 composite and applicationin adsorption desulfurization[J]. Journal of Petrochemical Universities, 2014, 27(3): 41-47.

[136] Li Z, Cui X, Ma J, et al. Preparation of granular X-type zeolite/activated carbon composite from elutrilithe by adding pitch and solid SiO₂ [J]. Materials Chemistry and Physics, 2014, 147(3): 1003-1008.

[137] Ma J, Tan J, Du X, et al. Effects of preparation parameters on the textural features of a granular zeolite/activated carbon composite material synthesized from elutrilithe and pitch[J]. Microporous and Mesoporous Materials, 2010, 132(3): 458-463.

[138] Jevremović A, Bober P, Mičušík M, et al. Synthesis and characterization of polyaniline/BEA zeolite composites and their application in nicosulfuron adsorption[J]. Microporous and Mesoporous Materials, 2019, 287: 234-245.

[139] Liaquat I, Munir R, Abbasi N A, et al. Exploring zeolite-based composites in adsorption and photocatalysis for toxic wastewater treatment: Preparation, mechanisms, and future perspectives[J]. Environmental Pollution, 2024, 349: 123922.

[140] Li R, Chong S, Altaf N, et al. Synthesis of ZSM-5/Siliceous zeolite composites for improvement of hydrophobic adsorption of volatile organic compounds[J]. Frontiers in Chemistry, 2019(505): 1-10.

[141] Li R, Xue T, Li Z, et al. Hierarchical structure ZSM-5/SBA-15 composite with improved hydrophobicity for adsorption-desorption behavior of toluene[J]. Chemical Engineering Journal, 2020, 392: 124861.

[142] Cejka J, Mintova S. Perspectives of micro/mesoporous composites in catalysis[J]. Catalysis Reviews, 2007, 49(4): 457-509.

[143] Cui T, Rajendran A, Fan H, et al. Review on hydrodesulfurization over zeolite-based catalysts[J]. Industrial & Engineering Chemistry Research, 2021, 60(8): 3295-3323.

[144] 刘鹏,沈健. ZSM-5-SBA-15复合分子筛制备及甲苯甲醇烷基化性能研究[J]. 燃料化学学报,2015,43(9): 1147-1152.

[145] Liu Peng, Shen Jian. Preparation of ZSM-5-SBA-15 composite molecular sieves and its performance for toluene alkylation with methanol[J]. Journal of Fuel Chemistry and Technology, 2015, 43(9): 1147-1152.

[146] Mohammed R R. Comparison study of adsorption of lead and methylene blue on zeolite, activated carbon and their composite materials[J]. Journal of Engineering, 2019, 25(8): 129-148.

[147] Halim A A, Aziz H A, Johari M A M, et al. Comparison study of ammonia and COD adsorption on zeolite, activated carbon and composite materials in landfill leachate treatment[J]. Desalination, 2010, 262(1): 31-35.

[148] Pizarro C, Escudey M, Bravo C, et al. Sulfate kinetics and adsorption studies on a zeolite/polyammonium cation composite for environmental remediation[J]. Minerals, 2021, 11(2): 1102180.

[149] Zadaka A D, Nasser A, Nir S, et al. Removal of methyl tertiary-butyl ether (MTBE) from water by polymer-zeolite composites[J]. Microporous and Mesoporous Materials, 2012, 151: 216-222.

[150] Gaffer A, Alkahlawy A A, Aman D. Magnetic zeolite-natural polymer composite for adsorption of chromium (Ⅵ)[J]. Egyptian Journal of Petroleum, 2017, 26(4): 995-999.

[151] Humelnicu D, Dinu M V, Drăgan E S. Adsorption characteristics of UO₂ ²⁺ and Th⁴⁺ ions from simulated radioactive solutions onto chitosan/clinoptilolite sorbents[J]. Journal of Hazardous Materials, 2011, 185(1): 447-455.

[152] Alshameri A, Yan C, Lei X. Enhancement of phosphate removal from water by TiO₂/Yemeni natural zeolite: preparation, characterization and thermodynamic[J]. Microporous and Mesoporous Materials, 2014, 196: 145-157.

[153] Kim J, Lee C, Kim W, et al. Adsorption equilibria of water vapor on alumina, zeolite 13X, and a zeolite X/activated carbon composite[J]. Journal of Chemical & Engineering Data, 2003, 48(1): 137-141.

[154] Wu S, Wang Y, Sun C, et al. Novel preparation of binder-free Y/ZSM-5 zeolite composites for VOCs adsorption[J]. Chemical Engineering Journal, 2021, 417: 129172.

[155] Milojević R M, Bajuk B D, Nedić V B, et al. Polyaniline/FeZSM-5 composites-Synthesis, characterization and their high catalytic activity for the oxidative degradation of herbicide glyphosate[J]. Microporous and Mesoporous Materials, 2018, 267: 68-79.

[156] Vu X H, Bentrup U, Hunger M, et al. Direct synthesis of nanosized-ZSM-5/SBA-15 analog composites from preformed ZSM-5 precursors for improved catalytic performance as cracking catalyst[J]. Journal of Materials Science, 2014, 49(16): 5676-5689.

[157] Chen F, Jin W, Cheng D, et al. Fabrication of AC@ZSM-5 core-shell particles and their performance in fischer-tropsch synthesis[J]. Journal of Chemical Technology & Biotechnology, 2013, 88(12): 2133-2140.

[158] Zhao Q, Qin B, Zheng J, et al. Core-shell structured zeolite-zeolite composites comprising Y zeolite cores and nano-β zeolite shells: synthesis and application in hydrocracking of VGO oil[J]. Chemical Engineering Journal, 2014, 257: 262-272.

[159] Wang A, Yu K, Gao D, et al. Hierarchically porous ZSM-5/SBA-15 composite: tuning pore structure and acidity for hydrodesulfurization of dibenzothiophene[J]. Fuel, 2024, 362: 130826.

[160] Ooi Y, Zakaria R, Mohamed A R, et al. Synthesis of composite material MCM-41/Beta and its catalytic performance in waste used palm oil cracking[J]. Applied Catalysis A: General, 2004, 274(1/2): 15-23.

[161] Liu X, Yang T, Bai P, et al. Y/MCM-41 composites assembled from nanocrystals[J]. Microporous and Mesoporous Materials, 2013, 181: 116-122.

[162] Diao Z, Wang L, Zhang X, et al. Catalytic cracking of supercritical n-dodecane over meso-HZSM-5@Al-MCM-41 zeolites[J]. Chemical Engineering Science, 2015, 135: 452-460.

[163] Zhang J, Fan W, Liu Y, et al. Synthesis and catalytic property of a Co²⁺-exchanged Beta/Y composite for the selective catalytic reduction of NO by CH₄ in the presence of excess oxygen[J]. Applied Catalysis B: Environmental, 2007, 76(1/2): 174-184.

基金资助

国家自然科学基金青年科学基金项目(22008255)

中央高校基本科研业务费项目(2024ZKPYHH08)