Journal article
Crystal Size-Dependent Framework Flexibility of a Prototypical Metal Organic Framework is Related to Metal Content: Zeolitic Imidazolate Framework-7
Materials advances, Vol.5(22), pp.9055-9060
10/23/2024
DOI: 10.1039/D4MA00804A
Appears in UI Libraries Support Open Access
Abstract
Crystal size engineering is an emerging strategy to modulate mechanical and gas adsorption properties of metal–organic frameworks (MOFs). Fundamental principles on how the properties of these materials with changes to size remain to be understood and explored. Here, supermicron-, micro-, and nano-sized single crystals of a prototypical MOF zeolitic imidazolate framework-7 (ZIF-7) were generated using solvothermal method. Atomic force microscopy (AFM) imaging revealed that nano- and micro-sized crystals exhibited rounded and prism-like morphologies, respectively. AFM nanoindentation was used to assess the stiffness (Young’s modulus) of the rounded and prism-like crystals as a function of crystal size. We demonstrate that the framework flexibility increases (Young’s modulus decreases) with crystal size reduction for both morphologies, which can be attributed to a larger number of point defects (missing metal nodes and/or missing linkers) for smaller crystals. Remarkably, scanning electron microscopy (SEM) energy dispersive X-ray spectroscopy measurements on individual prism-like micro-sized crystals of various sizes revealed a decreasing trend in the Zn/C ratio with the crystal size reduction. Collectively, the size-dependent SEM and AFM characterizations suggest that smaller crystals have lower relative metal content via a larger number of missing metal nodes defects. Our findings highlight how mechanical properties of MOFs can vary significantly as a function of crystal size likely due to variable and size-dependent number of missing metal nodes defects. Such size-dependent behavior especially towards nanoscale is thus important to consider for a rational design of various functional crystalline materials.
Details
- Title: Subtitle
- Crystal Size-Dependent Framework Flexibility of a Prototypical Metal Organic Framework is Related to Metal Content: Zeolitic Imidazolate Framework-7
- Creators
- Akalanka B. EkanayakeAl TibaLeonard R MacGillivrayAlexei V Tivanski
- Resource Type
- Journal article
- Publication Details
- Materials advances, Vol.5(22), pp.9055-9060
- Publisher
- Royal Society of Chemistry
- DOI
- 10.1039/D4MA00804A
- ISSN
- 2633-5409
- eISSN
- 2633-5409
- Language
- English
- Date published
- 10/23/2024
- Academic Unit
- Chemistry
- Record Identifier
- 9984740858102771
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