Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks

Abstract

Flexible metal–organic frameworks (MOFs) exhibiting adsorption-induced structural transition can revolutionise adsorption separation processes, including CO₂ separation, which has become increasingly important in recent years. However, the kinetics of this structural transition remains poorly understood despite being crucial to process design. Here, the CO₂-induced gate opening of ELM-11 ([Cu(BF₄)₂(4, 4’-bipyridine)₂]n) is investigated by time-resolved in situ X-ray powder diffraction, and a theoretical kinetic model of this process is developed to gain atomistic insight into the transition dynamics. The thus-developed model consists of the differential pressure from the gate opening (indicating the ease of structural transition) and reaction model terms (indicating the transition propagation within the crystal). The reaction model of ELM-11 is an autocatalytic reaction with two pathways for CO₂ penetration of the framework. Moreover, gas adsorption analyses of two other flexible MOFs with different flexibilities indicate that the kinetics of the adsorption-induced structural transition is highly dependent on framework structure.