International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan.
Key Laboratory of Eco-chemical Engineering College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China.
Adv Mater. 2019 Mar;31(11):e1804903. doi: 10.1002/adma.201804903. Epub 2019 Jan 13.
Hollow materials derived from metal-organic frameworks (MOFs), by virtue of their controllable configuration, composition, porosity, and specific surface area, have shown fascinating physicochemical properties and widespread applications, especially in electrochemical energy storage and conversion. Here, the recent advances in the controllable synthesis are discussed, mainly focusing on the conversion mechanisms from MOFs to hollow-structured materials. The synthetic strategies of MOF-derived hollow-structured materials are broadly sorted into two categories: the controllable synthesis of hollow MOFs and subsequent pyrolysis into functional materials, and the controllable conversion of solid MOFs with predesigned composition and morphology into hollow structures. Based on the formation processes of hollow MOFs and the conversion processes of solid MOFs, the synthetic strategies are further conceptually grouped into six categories: template-mediated assembly, stepped dissolution-regrowth, selective chemical etching, interfacial ion exchange, heterogeneous contraction, and self-catalytic pyrolysis. By analyzing and discussing 14 types of reaction processes in detail, a systematic mechanism of conversion from MOFs to hollow-structured materials is exhibited. Afterward, the applications of these hollow structures as electrode materials for lithium-ion batteries, hybrid supercapacitors, and electrocatalysis are presented. Finally, an outlook on the emergent challenges and future developments in terms of their controllable fabrications and electrochemical applications is further discussed.
由金属有机骨架（MOFs）衍生的中空材料，由于其可控制备的结构、组成、孔隙率和比表面积，表现出迷人的物理化学性质和广泛的应用，特别是在电化学储能和转化领域。本文主要讨论了可控合成方面的最新进展，重点关注从 MOFs 到中空结构材料的转化机制。MOF 衍生的中空结构材料的合成策略广泛分为两类：中空 MOFs 的可控合成和随后热解成功能性材料，以及具有预定组成和形貌的固态 MOFs 的可控转化为中空结构。基于中空 MOFs 的形成过程和固态 MOFs 的转化过程，进一步将合成策略概念性地分为六类：模板介导组装、分步溶解-再生长、选择性化学刻蚀、界面离子交换、异质收缩和自催化热解。通过详细分析和讨论 14 种反应过程，展示了从 MOFs 到中空结构材料的转化机制。随后，介绍了这些中空结构作为锂离子电池、混合超级电容器和电催化的电极材料的应用。最后，进一步讨论了在可控制备和电化学应用方面所面临的新兴挑战和未来发展。
