Structural dynamics of a metal–organic framework induced by CO2 migration in its non-uniform porous structure

Abstract

Stimuli-responsive behaviors of flexible metal–organic frameworks (MOFs) make these materials promising in a wide variety of applications such as gas separation, drug delivery, and molecular sensing. Considerable efforts have been made over the last decade to understand the structural changes of flexible MOFs in response to external stimuli. Uniform pore deformation has been used as the general description. However, recent advances in synthesizing MOFs with non-uniform porous structures, i.e. with multiple types of pores which vary in size, shape, and environment, challenge the adequacy of this description. Here, we demonstrate that the CO₂-adsorption-stimulated structural change of a flexible MOF, ZIF-7, is induced by CO₂ migration in its non-uniform porous structure rather than by the proactive opening of one type of its guest-hosting pores. Structural dynamics induced by guest migration in non-uniform porous structures is rare among the enormous number of MOFs discovered and detailed characterization is very limited in the literature. The concept presented in this work provides new insights into MOF flexibility.

Metal–organic frameworks that undergo structural transitions in response to external stimuli are promising for gas storage, but the mechanisms of such dynamics are poorly understood. Here the authors show that the structural transformation of ZIF-7 is induced by CO₂ migration through its non-uniform porous structure.