Responses of Defect-Rich Zr-Based Metal-Organic Frameworks toward NH3 Adsorption
Tatchamapan Yoskamtorn1, Pu Zhao1, Xin-Ping Wu2
1Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford OX1 3QR, U.K.
Journal of the American Chemical Society
|February 17, 2021
Summary
Functional linkers in zirconium-based metal-organic frameworks (MOFs) significantly influence ammonia adsorption. Modifying linkers alters MOF properties like porosity and flexibility, enabling tailored material responses.
Area of Science:
- Materials Science
- Chemistry
- Nanotechnology
Background:
- Metal-organic frameworks (MOFs) exhibit stimulus-responsive structural changes crucial for smart materials.
- Understanding these responses is key for applications in gas storage, drug delivery, and sensing.
Purpose of the Study:
- To investigate the impact of functional linkers on the ammonia adsorption behavior of defect-rich Zr-based MOFs.
- To elucidate how linker modification influences structural responses to ammonia and temperature.
Main Methods:
- Neutron and synchrotron diffraction
- Rietveld refinement
- Density functional theory (DFT) calculations
Main Results:
- Zr-based MOFs (UiO-67 and UiO-bpydc) show linker-dependent ammonia affinity.
- Bipyridine linkers dramatically alter ammonia adsorption profiles compared to phenyl linkers.
- Ammonia incorporation induces linker dynamics and affects hydrogen-bonding networks.
- Temperature influences ammonia-induced linker motions.
Conclusions:
- Functional linkers are critical for tuning MOF properties like gate-controlled porosity and structural rigidity.
- Molecular-level control over MOF properties is achievable by modifying linker structure and guest molecule interactions.
- Structural flexibility of linkers is sensitive to the type and amount of guest molecules.
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