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Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
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Identifying pathways to metal-organic framework collapse during solvent activation with molecular simulations.
Joseph R H Manning1,2,3, Gaël Donval1, Mat Tolladay1
1Centre for Integrated Materials, Processes and Structures, Department of Chemical Engineering, University of Bath UK T.Duren@bath.ac.uk.
Journal of Materials Chemistry. A
|December 7, 2023
Summary
Understanding metal-organic framework (MOF) activation is key to preventing framework collapse. Simulations reveal solvent mesophase formation causes capillary stress, explaining collapse and guiding better MOF activation protocols.
Area of Science:
- Materials Science
- Chemical Engineering
- Computational Chemistry
Background:
- Metal-organic frameworks (MOFs) are versatile nanoporous materials with broad applications.
- MOF activation, the removal of synthesis solvents, is crucial for accessing pore space.
- Framework collapse during activation hinders MOF utilization, with the underlying mechanism poorly understood.
Purpose of the Study:
- To elucidate the mechanism of MOF activation-collapse.
- To identify factors influencing solvent removal and framework stability.
- To enable the development of improved MOF activation protocols.
Main Methods:
- Simulations of solvent desorption using grand-canonical Monte Carlo and free energy perturbation.
- Framing MOF activation as a fluid desorption process.
- Investigating activation in the isoreticular metal organic framework (IRMOF) family with various solvents.
Main Results:
- Identified two solvent desorption pathways: uniform desorption and mesophase formation.
- Demonstrated that solvent mesophases induce capillary stresses, leading to framework collapse.
- Found increased activation energy with larger pore sizes and connectivity due to stable solvent mesophases.
Conclusions:
- Solvent mesophase formation is a primary cause of MOF activation-collapse.
- Simulation results align with and explain experimental observations.
- This work facilitates screening of MOF activation solvents and conditions for accelerated MOF development.
