In this study, two zeolitic imidazolate frameworks (ZIFs) called ZIF-4 and ZIF-zni (zni is the network topology) were characterized by sorption studies regarding their paraffin/olefin separation potential. In particular, equilibrated pure and mixed gas adsorption isotherms of ethane and ethene were recorded at 293 K up to 3 MPa. ZIF-4 exhibits selectivities for ethane in the range of 1.5–3, which is promising for continuous pressure swing adsorption (PSA). ZIF-4 shows high cycle stability with promising separation potential regarding ethane, which results in purification of the more industrial desired olefin. Furthermore, both ZIF materials were implemented in Matrimid to prepare a mixed matrix membrane (MMM) and were used in the continuous separation of a propane/propene mixture. The separation performance of the neat polymer is drastically increased after embedding porous ZIF-4 crystals in the Matrimid matrix, especially at higher feed pressures (3–5 barg). Due to the smaller kinetic diameter of the olefin, the permeability is higher compared to the paraffin.
This study presents the design, preparation, and characterization of thirty new medium-entropy alloys (MEAs) in three systems: Al-Ti-Nb-Zr, Al-Ti-Nb-V, and Al-Ti-Nb-Hf. The hardness of the alloys ranged from 320 to 800 HV0.3. Among the alloys studied, Al15Ti40Nb30Zr15 exhibited the highest-reversible hydrogen storage capacity (1.03 wt.%), with an H/M value of 0.68, comparable to LaNi5, but with a reduced density (5.11 g·cm−3) and without rare earth elements. This study further reveals a strong correlation between hardness and hydrogen absorption/desorption; higher hardness is responsible for reduced hydrogen uptake. This finding highlights the interplay between a material’s properties and hydrogen storage behavior in MEAs, and has implications for the development of efficient hydrogen storage materials.
The rate of sorption of n-butane on the structurally flexible metal-organic framework [Cu2(H-Me-trz-ia)2], including its complete structural transition between a narrow-pore phase and a large-pore phase, was studied by sorption gravimetry, IR spectroscopy, and powder X-ray diffraction at close to ambient temperature (283, 298, and 313 K). The uptake curves reveal complex interactions of adsorption on the outer surface of MOF particles, structural transition, of which the overall rate depends on several factors, including pressure step, temperature, as well as particle size, and the subsequent diffusion into newly opened pores. With the aid of a kinetic model based on the linear driving force (LDF) approach, both rates of diffusion and structural transition were studied independently of each other. It is shown that temperature and applied pressure steps have a strong effect on the rate of structural transition and thus, the overall velocity of gas uptake. For pressure steps close to the upper boundary of the gate-opening, the rate of structural transition is drastically reduced. This feature enables a fine-tuning of the overall velocity of sorption, which can even turn into anti-Arrhenius behavior.
The analysis of empirical sorption equilibrium datasets is still vital to gain insights into material–property relationships as computational methods remain in development, especially for complex materials such as flexible MOFs. Therefore, the Dubinin-based universal adsorption theory (D-UAT) was revisited and evaluated as a simple visualization, analysis, and prediction tool for sorption equilibrium data. Within the theory, gas properties are normalized into corresponding states using the critical temperatures of the respective sorptives. The study shows theoretically and experimentally that the D-UAT is able to condense differences of sorption data visualized in reduced Dubinin plots to just three governing parameters: (a) the accessible pore volume, (b) the reduced enthalpy of sorption, and (c) the framework’s reduced free energy differences (in case of flexible behavior). This makes the theory a fast visualization and analysis tool, the use as a prediction tool depends on rough assumptions, and thus is not recommended.
Single gas sorption experiments with the C4-hydrocarbons n-butane, iso-butane, 1-butene and iso-butene on the flexible MOFs Cu-IHMe-pw and Cu-IHEt-pw were carried out with both thermodynamic equilibrium and overall sorption kinetics. Subsequent static binary gas mixture experiments of n-butane and iso-butane unveil a complex dependence of the overall selectivity on sorption enthalpy, rate of structural transition as well as steric effects. A thermodynamic separation favoring iso-butane as well as kinetic separation favoring n-butane are possible within Cu-IHMe-pw while complete size exclusion of iso-butane is achieved in Cu-IHEt-pw. This proof-of-concept study shows that the structural flexibility offers additional levers for the precise modulation of the separation mechanisms for complex mixtures with similar chemical and physical properties with real selectivities of >10.
This study introduces an innovative approach to alloy design by experimentally validating the semi-empirical concept of Griessen and Driessen, which predicts the hydrogen affinity of solid solutions. The work focuses on designing and synthesizing four equiatomic high-entropy alloys (HEAs) with compositions tailored to exhibit highly endothermic enthalpies of solution and formation, resulting in resistance to hydrogen absorption. Unlike conventional studies that prioritize hydrogen storage capacity, this research uniquely targets alloys optimized for minimal hydrogen interaction, addressing critical needs in hydrogen storage and transportation technologies prone to hydrogen embrittlement. Experimental results confirm the negligible hydrogen absorption of these alloys, with a maximum of 0.23 wt.% (H/M = 0.13) at 2 MPa and 175 °C. This study not only demonstrates the applicability of a theoretical model to guide alloy design but also highlights the potential of these materials for low-pressure hydrogen storage systems, where mechanical integrity and resistance to hydrogen degradation are paramount. The findings bridge the gap between theoretical predictions and practical applications, offering a novel perspective on alloy development for hydrogen-related technologies.