International Center for Materials Nanoarchitechtonics, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
Chem Soc Rev. 2021 Mar 7;50(5):2927-2953. doi: 10.1039/c9cs00813f. Epub 2021 Jan 22.
Template-directing strategies for synthesising metal-organic frameworks (MOFs) have brought about new frontiers in materials chemistry due to the possibility of applying control over crystal growth, morphology and secondarily generated pores. In particular, hard templates have resulted in performance breakthroughs in catalysis, secondary ion batteries, supercapacitance, drug delivery and molecular sieving by offering facile routes for maximising the surface areas of shape-directed MOFs. In this tutorial review, a variety of hard templates employed to direct MOFs' growth into superior nano-architectures with enhanced functionalities are discussed. Hard templates discussed here include polymers, silica nanostructures, metal oxides, layered metal hydroxides, noble metals, graphene, zeolites and MOFs themselves. These templates can be divided into three broad categories: sacrificial, semi-sacrificial and non-sacrificial templates. We elaborate on the rationale behind the choice of nanomaterials as hard templates, how hard templates direct the synthesis of MOFs, how sacrificial hard templates can be removed from the final product and what the enhanced functionalities of hard-templated MOFs are. In the case of non-sacrificial hard-templates, synergistic effects arising from the coexistence of the MOF and the hard template will also be reviewed.
模板导向策略在金属-有机骨架（MOFs）的合成中带来了材料化学的新前沿，因为有可能控制晶体生长、形态和次生孔。特别是硬模板通过为形状导向的 MOFs 提供最大化表面积的简便途径，在催化、二次离子电池、超级电容器、药物输送和分子筛方面取得了性能突破。在本教程综述中，讨论了各种用于将 MOFs 的生长引导到具有增强功能的优越纳米结构的硬模板。这里讨论的硬模板包括聚合物、硅纳米结构、金属氧化物、层状金属氢氧化物、贵金属、石墨烯、沸石和 MOFs 本身。这些模板可以分为三大类：牺牲、半牺牲和非牺牲模板。我们详细阐述了选择纳米材料作为硬模板的原理、硬模板如何指导 MOFs 的合成、牺牲性硬模板如何从最终产物中去除以及硬模板化 MOFs 的增强功能。对于非牺牲性硬模板，还将综述 MOF 和硬模板共存产生的协同效应。
