Tuning porosity in macroscopic monolithic metal-organic frameworks for exceptional natural gas storage.

Widespread access to greener energy is required in order to mitigate the effects of climate change. A significant barrier to cleaner natural gas usage lies in the safety/efficiency limitations of storage technology. Despite highly porous metal-organic frameworks (MOFs) demonstrating record-breaking gas-storage capacities, their conventionally powdered morphology renders them non-viable. Traditional powder shaping utilising high pressure or chemical binders collapses porosity or creates low-density structures with reduced volumetric adsorption capacity. Here, we report the engineering of one of the most stable MOFs, Zr-UiO-66, without applying pressure or binders. The process yields centimetre-sized monoliths, displaying high microporosity and bulk density. We report the inclusion of variable, narrow mesopore volumes to the monoliths' macrostructure and use this to optimise the pore-size distribution for gas uptake. The optimised mixed meso/microporous monoliths demonstrate Type II adsorption isotherms to achieve benchmark volumetric working capacities for methane and carbon dioxide. This represents a critical advance in the design of air-stable, conformed MOFs for commercial gas storage.

Combined use of DGT and transplanted shrimp (Litopenaeus vannamei) to assess the bioavailable metals of complex contamination: implications for implementing bioavailability-based water quality criteria.

The diffusive gradients in thin films (DGT) were field deployed alongside the shrimp Litopenaeus vannamei at seven sites with different levels of contamination to assess the potentially bioavailable and toxic fraction of metal contaminants. After 7 days of exposure, several antioxidant biomarkers were quantified in hepatopancreas of exposed shrimps, and tissue levels as well as the total, dissolved, and DGT-labile concentrations of metal contaminants were determined in the pooled site samples. The results showed that the caged shrimps had high tissue contaminant concentrations and significantly inhibited antioxidant responses at the more contaminated sites. DGT-labile metal concentrations provided better spatial resolution of differences in metal contamination when compared with traditional bottle sampling and transplanted shrimp. The total, dissolved, and DGT-labile metal fractions were used to evaluate the potential bioavailability of metal contaminants, comparing with metal accumulation and further linking to antioxidant biomarker responses in tissues of exposed shrimps. Regression analysis showed the significant correlations between DGT-Cu concentrations and tissue-Cu and activities of some biomarker responses in the shrimp hepatopancreas. This indicated that DGT-labile Cu concentrations provided the better prediction of produced biological effects and of the bioavailability than the total or dissolved concentrations. The study supports the use of methods combining transplanted organisms and passive sampling for assessing the chemical and ecotoxicological status of aqueous environments and demonstrates the capability of the DGT technique as a powerful tool for measuring the bioavailability-based water quality in variable coastal environments.