(326a) Adsorption-Induced Deformation of Nanoporous Materials: From MMS to MOF

Neimark, A. V., Rutgers, The State University of New Jersey
Gor, G., Rutgers, The State University of New Jersey
Kan, Y., Rutgers, The State University of New Jersey
Coudert, F., Chimie ParisTech (École nationale supérieure de chimie de Paris)
Boutin, A., École Normale Supérieure
Fuchs, A. H., CNRS

Phenomenon of adsorption-induced deformation attracted recently a considerable attention owing to its relevance to
practical problems of mechanical stability and integrity of novel nanoporous materials. Micro- and mesoporous materials
find numerous applications as selective adsorbents and catalysts, substrates for biosensors and drug delivery,
membranes and films in various nanotechnologies, which involve fluids adsorbed or confined to nanoscale pores within
rigid or compliant solid matrixes. Guest molecules adsorbed in pores cause a substantial stress in the host matrix leading
to its contraction or swelling. Although various experimental manifestations of adsorption-induced deformation have been
known for a long time, a rigorous theoretical description of this phenomenon is lacking. A general thermodynamic
approach is suggested for predicting adsorption stress and respective deformation in various microporous and
mesoporous materials. The proposed method is based on the analysis of adsorption isotherms by means of molecular
simulations, density functional theory, and empirical models. The main focus is made on contraction-expansion cycles in
microporous zeolites and active carbons [1, 2], and on hysteretic deformations in the course of capillary condensation
and desorption in mesoporous molecular sieves (MMS) and structural transformations known as breathing transitions in
metal-organic frameworks (MOF) [3].
[1] P.I. Ravikovitch and A.V. Neimark, - Density Functional Theory Model of Adsorption Deformation – Langmuir, 2006,
V.22, p.p. 10864-10868. [2] P. Kowalczyk, A. Ciach, and A.V. Neimark, - Adsorption-induced deformation of
microporous carbons: pore size distribution effect, - Langmuir, 2008, V. 24, p.6603-6608. [3] A. V. Neimark, F.X.
Coudert, A. Boutin, and A. H. Fuchs, - Stress-based model for the breathing of metal–organic frameworks, J. Physical
Chemistry Letters, 2010, V.1, p.445–449. [4] A. V. Neimark, F.X. Coudert,  C. Triguero, A. Boutin, A. H. Fuchs, I. Beurroies, and R. Denoyel, - Structural Transitions in MIL-53 (Cr): View from Outside and Inside, - Langmuir, 2011, V.27, p.4734–4741[6] G. Yu. Gor and A.V. Neimark, - Adsorption-Induced Deformation of Mesoporous Solids, - Langmuir, 2010, V.26, p.13021–13027.