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Structural transitions in MIL-53 (Cr): view from outside and inside.
Alexander V Neimark1, François-Xavier Coudert, Carles Triguero
1Chimie ParisTech (École Nationale Supérieure de Chimie de Paris), CNRS and Université Pierre et Marie Curie, Paris, France. aneimark@rutgers.edu
Langmuir : the ACS Journal of Surfaces and Colloids
|March 23, 2011
Summary
We unified the thermodynamic description of MIL-53 (Cr) breathing transitions, linking guest adsorption stress to mechanical compression. This reveals insights into structural transformations in soft porous crystals (SPCs).
Area of Science:
- Materials Science
- Thermodynamics
- Crystallography
Background:
- MIL-53 (Cr) exhibits breathing transitions between large pore (lp) and narrow pore (np) phases.
- These transitions are observed during guest molecule adsorption and mechanical compression.
Purpose of the Study:
- To present a unified thermodynamic description of MIL-53 (Cr) breathing transitions.
- To correlate adsorption-induced stress with external mechanical pressure for phase transformations.
Main Methods:
- Revisiting experimental data from mercury intrusion porosimetry.
- Analyzing in situ X-ray diffraction (XRD) data during CO(2) adsorption.
Main Results:
- Adsorption stress magnitude matches external pressure for lp-np phase transitions.
- MIL-53 (Cr) shows small reversible elastic (2-4%) and significant irreversible plastic deformations (up to ~40% volume change) during breathing.
- Pronounced hysteresis is observed in the breathing transition.
Conclusions:
- The study provides a unified thermodynamic framework for understanding MIL-53 (Cr) breathing.
- Results elucidate the nature of structural transformations in MIL-53 (Cr) and other soft porous crystals (SPCs).
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