Flexible porous frameworks are at the forefront of materials research. A unique feature is their ability to open and close their pores in an adaptive manner induced by chemical and physical stimuli. Such enzyme‐like selective recognition offers a wide range of functions ranging from gas storage and separation to sensing, actuation, mechanical energy storage and catalysis. However, the factors affecting switchability are poorly understood. In particular, the role of building blocks, as well as secondary factors (crystal size, defects, cooperativity) and the role of host–guest interactions, profit from systematic investigations of an idealized model by advanced analytical techniques and simulations. The review describes an integrated approach targeting the deliberate design of pillared layer metal–organic frameworks as idealized model materials for the analysis of critical factors affecting framework dynamics and summarizes the resulting progress in their understanding and application.

Variation of the crystallite size in flexible porous coordination polymers can significantly influence or even drastically change the flexibility characteristics. The impact of crystal morphology, however, on the dynamic properties of flexible metal-organic frameworks (MOFs) is poorly investigated so far. In the present work, we systematically modulated the particle size of a model gate pressure MOF (DUT-8(Ni), Ni2(2,6-ndc)2(dabco), 2,6-ndc−2,6-naphthalenedicarboxylate, dabco−1,4-diazabicyclo[2.2.2]octane) and investigated the influence of the aspect ratio, length, and width of anisotropically shaped crystals on the gate opening characteristics. DUT-8 is a member of the pillared-layer MOF family, showing reversible structural transition, i.e., upon nitrogen physisorption at 77 K. The framework crystalizes as rod-like shaped crystals in conventional synthesis. To understand which particular crystal surfaces dominate the phenomena observed, crystals similar in size and differing in morphology were involved in a systematic study. The analysis of the data shows that the width of the rods (corresponding to the crystallographic directions along the layer) represents a critical parameter governing the dynamic properties upon adsorption of nitrogen at 77 K. This observation is related to the anisotropy of the channel-like pore system and the nucleation mechanism of the solid-solid phase transition triggered by gas adsorption.

The pillared layer framework DUT-8(Zn) (Zn2(2,6-ndc)2(dabco), 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane, DUT = Dresden University of Technology) is a prototypical switchable MOF, showing characteristic adsorption and desorption induced open...

In this work, amphoteric cryogels based on N,N-dimethyl acrylamide, methacrylic acid and allylamine, crosslinked by N,N-methylenebisacrylamide were synthesized by free-radical polymerization in cryo-conditions. The synthesized cryogels were used for the removal of cadmium ions from aqueous solutions under different pH values. The chemical structure was studied by FTIR, porosity by nitrogen adsorption and morphology by scanning electron microscopy and texture analyzer. The amphoteric properties of cryogels were studied by zeta potential measurements. Adsorption tests revealed that cryogels exhibit 3 times higher adsorption capacity at pH 6.0 than at pH 4.0. The maximum adsorption capacity of the amphoteric cryogels for Cd2+ was 113 mg/g, at pH 6.0 and initial Cd2+ concentration 100 ppm. The results suggest that the predominant removal mechanism is ion exchange between sodium, which initially presents in the structure of the cryogel, and cadmium from the aqueous phase. Recovery studies suggested that the cryogels used can be regenerated and efficiently reused.