Breathing porous liquids based on responsive metal-organic framework particles

Responsive metal-organic frameworks (MOFs) that display sigmoidal gas sorption isotherms triggered by discrete gas pressure-induced structural transformations are highly promising materials for energy related applications. However, their lack of transportability via continuous flow hinders their application in systems and designs that rely on liquid agents. We herein present examples of responsive liquid systems which exhibit a breathing behaviour and show step-shaped gas sorption isotherms, akin to the distinct oxygen saturation curve of haemoglobin in blood. Dispersions of flexible MOF nanocrystals in a size-excluded silicone oil form stable porous liquids exhibiting gated uptake for CO2, propane and propylene, as characterized by sigmoidal gas sorption isotherms with distinct transition steps. In situ X-ray diffraction studies show that the sigmoidal gas sorption curve is caused by a narrow pore to large pore phase transformation of the flexible MOF nanocrystals, which respond to gas pressure despite being dispersed in silicone oil. Given the established flexible nature and tunability of a range of MOFs, these results herald the advent of breathing porous liquids whose sorption properties can be tuned rationally for a variety of technological applications

A new approach to enhancing the CO2 capture performance of defective UiO-66 via post-synthetic defect exchange

Zirconium-based metal-organic frameworks (Zr-MOFs) are a subclass of MOFs known for their remarkable stability, especially in the presence of water. This makes them extremely attractive for practical applications, including CO2 capture from industrial emission sources; however, the CO2 adsorption capacity of Zr-MOFs is moderate compared to that of the best performing MOFs reported to date. Functionalization of Zr-MOFs with amino groups has been demonstrated to increase their affinity for CO2. In this work, we assessed the potential of post-synthetic defect exchange (PSDE) as an alternative approach to introduce amino functionalities at missing-cluster defective sites in formic acid modulated UiO-66. Both pyridine-containing (picolinic acid and nicotinic acid) and aniline-containing (3-aminobenzoic acid and anthranilic acid) monocarboxylates were integrated within defective UiO-66 with this method. Non-defective UiO-66 modified with linkers bearing the same amino groups (2,5-pyridinedicarboxylic acid and 2-aminoterephthalic acid) were prepared by classical post-synthetic ligand exchange (PSE), in order to compare the effect of introducing functionalities at defective sites versus installing them on the backbone. PSDE reduces the porosity of defective UiO-66, but improves both the CO2 uptake and the CO2/N2 selectivity, whereas PSE has no effect on the porosity of non-defective UiO-66, improving the CO2 uptake but leaving selectivity unchanged. Modification of defective UiO-66 with benzoic acid reveals that pore size reduction is the main factor responsible for the observed uptake improvement, whereas the presence of nitrogen atoms in the pores seems to be beneficial for increasing selectivity

CO₂ Capture Partner Molecules in Highly Loaded PEI Sorbents

Decoupling amine loading from diffusion resistance is one of the main challenges in the development of immobilized amine CO₂ sorbents. Water has been reported to serve this goal, alleviating CO₂ diffusional hindrance in highly loaded amine sorbents. Acting as a mass transport facilitator, water is not the only partner molecule able to enhance bulk CO₂ diffusion. Herein, we show that the enhancing effect of methanol is comparable to that of water in polyethylenimine-based sorbents. Other molecules, such as ethanol, isopropanol, and chloroform, were also examined but did not appear to facilitate CO₂ transport and uptake. Based on a comparison of the Hansen solubility parameters of these molecules, it appears that polarity plays a crucial role in enhancing CO₂ diffusion together with molecular hindrance and hydrogen bonding to a lesser extent

Zeolite development from fly ash and utilization in lignite mine-water treatment

Abstract Fly ash from two lignite-fed power stations in Greece (Megalopolis and Meliti) has been utilized to synthesize zeolitic materials with upgraded adsorption capacity. Two different siliceous fly ash samples were subjected to hydrothermal treatment at fixed solid/liquid ratio and constant temperature. The zeolitic products have been characterized for their microstructure, chemical, and mineralogical composition by means of SEM, AAS, and XRD, respectively. The primary zeolitic crystals identified were phillipsite and thomsonite, in Megalopolis and Meliti fly ash, respectively. In light of their prospective utilization as liquid-phase sorbents, the specific surface area and porosity of materials were also determined, by means of N2-porosimetry. The zeolitic samples were tested for their actual heavy metal-removal capacity by water sampled from active lignite mines in Northern Greece. Artificial aquatic samples with known concentration of heavy metals (Cd, Cr, Cu, Ni, Pb, and Zn) were also tested, showing that the synthetic zeolitic materials are good to uptake a wide variety of potential pollutants with up to 100% efficiency. The efficiency of the synthetic zeolitic materials was comparatively assessed, showing that the more intense the presence of phillipsite in the synthetic materials, the greater the uptake rates for certain groups of trace elements

Breathing porous liquids based on responsive metal-organic framework particles

Responsive metal-organic frameworks (MOFs) that display sigmoidal isotherms triggered by discrete gas pressure-induced structural transformations are highly promising materials for energy related applications. However, their lack of transportability via continuous flow hinders their application in systems and designs that rely on liquid agents. We herein present examples of responsive liquid systems which exhibit a breathing behaviour and show step-shaped gas sorption isotherms, akin to the distinct oxygen saturation curve of haemoglobin in blood. Dispersions of flexible MOF nanocrystals in a size-excluded silicone oil form stable porous liquids exhibiting gated uptake for CO2, propane and propylene, as characterized by sigmoidal gas sorption isotherms with distinct transition steps. In situ X-ray diffraction studies show that the sigmoidal gas sorption curve is caused by a narrow pore to large pore phase transformation to the flexible MOF nanocrystals, which respond to gas pressure despite being dispersed in silicone oil. Given the established flexible nature and tunability of a range of MOFs, these results herald the advent of breathing porous liquids whose sorption properties can be tuned rationally for a variety of technological applications

Modulating Liquid–Liquid Transitions and Glass Formation in Zeolitic Imidazolate Frameworks by Decoration with Electron-Withdrawing Cyano Groups

The liquid phase of metal–organic frameworks (MOFs) is key for the preparation of melt-quenched bulk glasses as well as the shaping of these materials for various applications; however, only very few MOFs can be melted and transformed into stable glasses. Here, the solvothermal and mechanochemical preparation of a new series of functionalized derivatives of ZIF-4 (Zn(im)2, where im– = imidazolate and ZIF = zeolitic imidazolate framework) containing the cyano-functionalized imidazolate linkers CNim– (4-cynanoimidazolate) and dCNim– (4,5-dicyanoimidazolate) is reported. The strongly electron-withdrawing nature of the CN groups facilitates low-temperature melting of the materials (below 310 °C for some derivatives) and the formation of microporous ZIF glasses with remarkably low glass-transition temperatures (down to only about 250 °C) and strong resistance against recrystallization. Besides conventional ZIF-4, the CN-functionalized ZIFs are so far the only MOFs to show an exothermic framework collapse to a low-density liquid phase and a subsequent transition to a high-density liquid phase. By systematic adjustment of the fraction of cyano-functionalized linkers in the ZIFs, we derive fundamental insights into the thermodynamics of the unique polyamorphic nature of these glass formers as well as further design rules for the porosity of the ZIF glasses and the viscosity of their corresponding liquids. The results provide new insights into the unusual phenomenon of liquid–liquid transitions as well as a guide for the chemical diversification of meltable MOFs, likely with implications beyond the archetypal ZIF glass formers

Highly porous metal-organic framework liquids and glasses via a solvent-assisted linker exchange strategy of ZIF-8

By combining the porosity of crystalline metal-organic frameworks (MOFs) with the unique processability of the liquid state, melt-quenched MOF glasses offer exciting opportunities for molecular separation. However, progress in this field is limited by two factors. Firstly, only very few MOFs melt at elevated temperature and transform into stable glasses upon cooling of the corresponding MOF liquid. Secondly, the MOF glasses obtained thus far feature only very small porosities and extremely small pore sizes. Here we demonstrate solvent-assisted linker exchange (SALE) as a versatile method to prepare highly porous melt-quenched MOF glasses from the canonical ZIF-8. Two additional organic linkers are incorporated into the non-meltable ZIF-8, yielding high-entropy, linker-exchanged ZIF-8 derivatives undergoing crystal-to-liquid-to-glass phase transitions by thermal treatment. The ZIF-8 glasses demonstrate unprecedented porosities of about 25%, adsorb large amounts of technologically relevant C3 and C4 hydrocarbons, and feature high kinetic sorption selectivities for the separation of propylene from propane

Highly porous metal-organic framework liquids and glasses via a solvent-assisted linker exchange strategy of ZIF-8

Abstract By combining the porosity of crystalline metal-organic frameworks (MOFs) with the unique processability of the liquid state, melt-quenched MOF glasses offer exciting opportunities for molecular separation. However, progress in this field is limited by two factors. Firstly, only very few MOFs melt at elevated temperatures and transform into stable glasses upon cooling the corresponding MOF liquid. Secondly, the MOF glasses obtained thus far feature only very small porosities and very small pore sizes. Here, we demonstrate solvent-assisted linker exchange (SALE) as a versatile method to prepare highly porous melt-quenched MOF glasses from the canonical ZIF-8. Two additional organic linkers are incorporated into the non-meltable ZIF-8, yielding high-entropy, linker-exchanged ZIF-8 derivatives undergoing crystal-to-liquid-to-glass phase transitions by thermal treatment. The ZIF-8 glasses demonstrate specific pore volumes of about 0.2 cm3g–1, adsorb large amounts of technologically relevant C3 and C4 hydrocarbons, and feature high kinetic sorption selectivities for the separation of propylene from propane

Cooperative CO2_2 adsorption mechanism in a perfluorinated CeIV^{IV} -based metal organic framework

Adsorbents able to uptake large amounts of gases within a narrow range of pressure, i.e., phase-change adsorbents, are emerging as highly interesting systems to achieve excellent gas separation performances with little energy input for regeneration. A recently discovered phase-change metal–organic framework (MOF) adsorbent is F4_MIL-140A(Ce), based on Ce$^{IV}$ and tetrafluoroterephthalate. This MOF displays a non-hysteretic step-shaped CO$_2$ adsorption isotherm, reaching saturation in conditions of temperature and pressure compatible with real life application in post-combustion carbon capture, biogas upgrading and acetylene purification. Such peculiar behaviour is responsible for the exceptional CO$_2$/N$_2$ selectivity and reverse CO$_2$/C$_2$H$_2$ selectivity of F4_MIL-140A(Ce). Here, we combine data obtained from a wide pool of characterisation techniques – namely gas sorption analysis, in situ infrared spectroscopy, in situ powder X-ray diffraction, in situ X-ray absorption spectroscopy, multinuclear solid state nuclear magnetic resonance spectroscopy and adsorption microcalorimetry – with periodic density functional theory simulations to provide evidence for the existence of a unique cooperative CO$_2$ adsorption mechanism in F4_MIL-140A(Ce). Such mechanism involves the concerted rotation of perfluorinated aromatic rings when a threshold partial pressure of CO$_2$ is reached, opening the gate towards an adsorption site where CO$_2$ interacts with both open metal sites and the fluorine atoms of the linker