RESUMEN
Investigations into a thermally generated decarboxylation mechanism for metal site activation and the generation of mesopores in a carboxylate iron-based MOF, PCN-250, have been conducted. PCN-250 exhibits an interesting oxidation state change during thermal treatment under inert atmospheres or vacuum conditions, transitioning from an Fe(iii)3 cluster to a Fe(ii)Fe(iii)2 cluster. To probe this redox event and discern a mechanism of activation, a combination of thermogravimetric analysis, gas sorption, scanning electron microscopy, 57Fe Mössbauer spectroscopy, gas chromatography-mass spectrometry, and X-ray diffraction studies were conducted. The results suggest that the iron-site activation occurs due to ligand decarboxylation above 200 °C. This is also consistent with the generation of a missing cluster mesoporous defect in the framework. The resulting mesoporous PCN-250 maintains high thermal stability, preserving crystallinity after multiple consecutive high-temperature regeneration cycles. Additionally, the thermally reduced PCN-250 shows improvements in the total uptake capacity of methane and CO2.
RESUMEN
Metal-Organic Frameworks (MOFs) have been intensively studied for applications such as gas storage, gas separation, catalysis, drug delivery, and more. Typically, the development of MOFs involves a post-synthetic solvent exchange process, which usually requires a significant investment of time, energy, labor, and resources. Herein, we propose a novel post-synthetic processing methodology for commercial and laboratory-scale MOFs called "Suspension Processing." Suspension processing is a non-destructive, agitation-based technique that provides efficient solvent exchange, pore cleaning, and surface defect removal in MOFs. Suspension processing has shown the capability to significantly improve the surface area and gas uptake properties of microporous MOFs, including PCN-250, UiO-66, and HKUST-1. Suspension processing displays improved time, energy, and labor efficiency, as well as considerably enhanced product quality. These findings confirm suspension processing as a straightforward methodology with applicability as a universal technique for the production of high-quality microporous materials.
RESUMEN
Metal-organic frameworks (MOFs) as methane adsorbents are highly promising materials for applications such as methane-powered vehicles, flare gas capture, and field natural gas separation. Pre- and post-synthetic modification of MOFs have been known to help improve both the overall methane uptake as well as the working capacity. Here, a post-synthetic modification strategy to non-covalently modify MOF adsorbents for the enhancement of the natural gas uptake for the MOF material is introduced. In this study, PCN-250 adsorbents were doped with C10 alkane and C14 fatty acid and their impact on the methane uptake capabilities was investigated. It was found that even trace amounts of heavy hydrocarbons could considerably enhance the raw methane uptake of the MOF while still being regenerable. The doped hydrocarbons are presumably located at the mesoporous defects of PCN-250, thus optimizing the framework-methane interactions. These findings reveal a general approach that can be used to modify the MOF absorbents, improving their ability to be sustainable and renewable natural gas adsorption platforms.
