Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 48, Pages 14417-14421Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201507588
Keywords
anisotropic etching; hollow particles; metal-organic frameworks; porosity; zeolitic-imidazolate frameworks
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Funding
- MINECO-Spain [PN MAT2012-30994, 2014-SGR-80]
- EU FP7 ERC-Co [615954]
- MINECO
- Generalitat de Catalunya
- Spanish MINECO through the Severo Ochoa Centers of Excellence Program [SEV-2013-0295]
- European Research Council (ERC) [615954] Funding Source: European Research Council (ERC)
- ICREA Funding Source: Custom
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Controlling the shape of metal-organic framework (MOF) crystals is important for understanding their crystallization and useful for myriad applications. However, despite the many advances in shaping of inorganic nanoparticles, post-synthetic shape control of MOFs and, in general, molecular crystals remains embryonic. Herein, we report using a simple wet-chemistry process at room temperature to control the anisotropic etching of colloidal ZIF-8 and ZIF-67 crystals. Our work enables uniform reshaping of these porous materials into unprecedented morphologies, including cubic and tetrahedral crystals, and even hollow boxes, by an acid-base reaction and subsequent sequestration of leached metal ions. Etching tests on these ZIFs reveal that etching occurs preferentially in the crystallographic directions richer in metal-ligand bonds; that, along these directions, the etching rate tends to be faster on the crystal surfaces of higher dimensionality; and that the etching can be modulated by adjusting the pH of the etchant solution.
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