Over the past two decades, advanced materials with hollow interiors have received significant attention in materials research owing to their great application potential across a vast number of technological fields. Though with great difficulty, multi‐shelled hollow metal–organic frameworks (MSHMs) have also been successfully synthesized in recent years. Herein, a rational shell‐by‐shell soft‐templating protocol has been devised to fabricate highly uniform multi‐shelled hollow cobalt‐imidazole‐based MOF (ZIF‐67). For the first time, it has become possible to endow mesoporosity to this new type of functional material (i.e., mesoporous MOFs). When used as carrier materials in catalytic reactions, in principle, these mesoporous MSHMs with high surface area not only improve the dispersity of metal nanoparticles (NPs), but also efficiently facilitate the mass diffusion of the reactions, resulting in enhanced catalyst activity. Moreover, the obtained MSHMs/M nanocomposites serve as base‐metal bifunctional catalysts for one‐pot oxidation‐Knoevenagel condensation cascade reaction, in which the MSHMs itself serves as a pristine active catalyst in addition to its role of catalyst support. The results demonstrate that excellent multifunctional catalysts can be achieved via preparing intrinsically microporous bulk MOFs into extrinsically mesoporous MSHMs which possess many structural merits that conventional bulk MOFs do not have.

中文翻译：

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用于催化应用的介孔多壳空心MOF的逐壳合成方法

在过去的二十年中，具有中空内部结构的先进材料由于其在众多技术领域中的巨大应用潜力，在材料研究中受到了广泛关注。尽管困难重重，但近年来也已成功地合成了多壳空心金属有机骨架（MSHM）。在这里，已经设计了一种合理的逐壳软模板协议，以制造高度均匀的多壳中空钴咪唑基MOF（ZIF-67）。首次有可能赋予这种新型功能材料（即中孔MOF）以中孔性。当用作催化反应的载体材料时，原则上，这些具有高表面积的中孔MSHM不仅可以改善金属纳米颗粒（NP）的分散性，而且还有效地促进了反应的质量扩散，从而提高了催化剂的活性。此外，获得的MSHMs / M纳米复合材料可作为单锅氧化-Knoevenagel缩合级联反应的贱金属双功能催化剂，其中MSHMs本身除了作为催化剂载体以外，还可用作原始活性催化剂。结果表明，通过将本征微孔本体MOFs制备为具有许多常规本体MOF所不具有的结构优点的外在中孔MSHM，可以实现优异的多功能催化剂。其中MSHMs本身除了起催化剂载体的作用外还用作原始活性催化剂。结果表明，通过将本征微孔本体MOFs制备为具有常规本体MOF所不具有的许多结构优点的外在中孔MSHM，可以得到优异的多功能催化剂。其中MSHMs本身除了起催化剂载体的作用外还用作原始活性催化剂。结果表明，通过将本征微孔本体MOFs制备为具有常规本体MOF所不具有的许多结构优点的外在中孔MSHM，可以得到优异的多功能催化剂。