Metal-organic frameworks (MOFs) with open metal sites enrich the population of O2 in the pores significantly and assist the Li-O2 reaction when employed as a cell electrode material. A primary capacity of 9420 mA h g(-1) is achieved in a cell with Mn-MOF-74; more than four times higher than the value obtained in a cell without an MOF.
Vacancies are common in solid materials, but it remains a challenge to introduce them at specific locations with controlled distributions. Here we report the creation of ordered metal vacancies and linker vacancies in a cubic metal-organic framework (MOF) based on Zn(II) and pyrazolecarboxylic acid by removing a quarter of the metal ions and half of the linkers. The MOF with ordered vacancies shows increased pore size, thus allowing large dye molecules to fit in the pores. Furthermore, by filling the vacancies with new metals and new linkers, eight new single-crystalline MOFs with multicomponents in absolute order are introduced. The capability of performing stepwise elimination and addition reactions systematically in extended solids without destroying the structural integrity has generated complex MOF structures which otherwise cannot be made.
A hydrogen-bonded organic framework (HOF) was constructed by avoiding potential π-π stacking of building blocks with robust and non-coplanar triptycene-based modules. The tailored-fitting interactions were demonstrated by the adsorption of fullerene with a concentration enrichment of ∼420 times in the pores.
Materials built from multiple constituents have revealed emerging properties that are beyond linear integration of those from single components. We report a mesoporous metal-organic framework made from three geometrically distinct metal-containing secondary building units (SBUs) as a result of topological induction. The combinations of the Cu-based triangular, Zn-based octahedral, and Zn-based square pyramidal SBUs have created four types of cages in the network, despite that only one organic linker pyrazolecarboxylate was used. The longest distance for molecules maneuvering inside the largest cage is 5.2 nm. Furthermore, the complex and diversified pore environments allow the installation of various new functionalities in the framework as well as the expedited Ag nanoparticle formation in the pores. As presented in the molecule movement diagram, the crystal has provided specific arrangements of cages and apertures with distinct chemical features for guests transporting between the pores.
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