Insights into the Mechanochemical Glass Formation of Zeolitic Imidazolate Frameworks.

Metal-organic framework (MOF) glasses, known for their potential in gas separation, optics, and solid-state electrolytes, benefit from the processability of their (supercooled) liquid state. Traditionally, MOF glasses are produced by heating MOF crystals to their melting point and then cooling the liquid MOF to room temperature under an inert atmosphere. While effective, this melt-quenching technique requires high energy due to the high temperatures involved. It also limits the scope of new material development by restricting the compositional range to only those combinations of metal ions and linkers that are highly thermally stable. An alternative, mechanical milling at room temperature, has demonstrated its capability to transform MOF crystals into amorphous phases. However, the specific conditions under which these amorphous phases exhibit glass-like behavior remain uncharted. In this study, we explore the mechanochemical amorphization and vitrification of a variety of zeolitic imidazolate frameworks (ZIFs) with diverse linkers and different metal ions (Zn2+, Co2+ and Cu2+) at room temperature. Our findings demonstrate that ZIFs capable of melting can be successfully converted into glasses through ball-milling. Remarkably, some non-meltable ZIFs can also be vitrified using the ball-milling technique, as highlighted by the preparation of the first Cu2+-based ZIF glass.

Quantification of gas-accessible microporosity in metal-organic framework glasses.

Metal-organic framework (MOF) glasses are a new class of glass materials with immense potential for applications ranging from gas separation to optics and solid electrolytes. Due to the inherent difficulty to determine the atomistic structure of amorphous glasses, the intrinsic structural porosity of MOF glasses is only poorly understood. Here, we investigate the porosity features (pore size and pore limiting diameter) of a series of prototypical MOF glass formers from the family of zeolitic imidazolate frameworks (ZIFs) and their corresponding glasses. CO2 sorption at 195 K allows quantifying the microporosity of these materials in their crystalline and glassy states, also providing excess to the micropore volume and the apparent density of the ZIF glasses. Additional hydrocarbon sorption data together with X-ray total scattering experiments prove that the porosity features of the ZIF glasses depend on the types of organic linkers. This allows formulating design principles for a targeted tuning of the intrinsic microporosity of MOF glasses. These principles are counterintuitive and contrary to those established for crystalline MOFs but show similarities to strategies previously developed for porous polymers.