Pore opening and breathing transitions in metal-organic frameworks: Coupling adsorption and deformation

TY - JOUR

T1 - Pore opening and breathing transitions in metal-organic frameworks

T2 - Coupling adsorption and deformation

AU - Formalik, Filip

AU - Neimark, Alexander V.

AU - Rogacka, Justyna

AU - Firlej, Lucyna

AU - Kuchta, Bogdan

N1 - Publisher Copyright: © 2020 The Authors

PY - 2020/10/15

Y1 - 2020/10/15

N2 - Soft porous crystals undergo large structural transformations under a variety of physical stimuli. Breathing-like transformations, occurring with a large volume change, have been associated with an existence of bi-stable or multi-stable crystal structures. Understanding of the mechanism of these transformations is essential for their potential applications in gas adsorption, separation and storage. However, the generic description is still missing. Here, we provide a detailed, multiscale qualitative and quantitative analysis of the adsorption-induced “breathing” transformations in two metal organic frameworks (MOFs): MIL-53(Al) which is a reference case of our approach, and recently synthesized JUK-8, which does not show any bistability without adsorbate. The proposed approach is based on atomistic simulations and does not require any empirical or adjustable parameters. It allows for a prediction of potential structural transformations in MOFs including the adsorption induced deformations derived from adsorption stress model. We also show that the quantitative agreement between calculated and experimental results critically depends on the quality of the dispersion energy correction. Our methodology represents a new, powerful tool for designing and screening of flexible materials, alternative and complimentary to experimental approaches.

AB - Soft porous crystals undergo large structural transformations under a variety of physical stimuli. Breathing-like transformations, occurring with a large volume change, have been associated with an existence of bi-stable or multi-stable crystal structures. Understanding of the mechanism of these transformations is essential for their potential applications in gas adsorption, separation and storage. However, the generic description is still missing. Here, we provide a detailed, multiscale qualitative and quantitative analysis of the adsorption-induced “breathing” transformations in two metal organic frameworks (MOFs): MIL-53(Al) which is a reference case of our approach, and recently synthesized JUK-8, which does not show any bistability without adsorbate. The proposed approach is based on atomistic simulations and does not require any empirical or adjustable parameters. It allows for a prediction of potential structural transformations in MOFs including the adsorption induced deformations derived from adsorption stress model. We also show that the quantitative agreement between calculated and experimental results critically depends on the quality of the dispersion energy correction. Our methodology represents a new, powerful tool for designing and screening of flexible materials, alternative and complimentary to experimental approaches.

KW - Metal-organic framework

KW - Osmotic potential

KW - Phase transformations

UR - https://www.scopus.com/pages/publications/85085941203

UR - https://www.scopus.com/pages/publications/85085941203#tab=citedBy

U2 - 10.1016/j.jcis.2020.05.105

DO - 10.1016/j.jcis.2020.05.105

M3 - Article

C2 - 32512398

SN - 0021-9797

VL - 578

SP - 77

EP - 88

JO - Journal of Colloid And Interface Science

JF - Journal of Colloid And Interface Science

ER -