Few hydrogen adsorbents balance high usable volumetric and gravimetric capacities. Although metal-organic frameworks (MOFs) have recently demonstrated progress in closing this gap, the large number of MOFs has hindered the identification of optimal materials. Here, a systematic assessment of published databases of real and hypothetical MOFs is presented. Nearly 500,000 compounds were screened computationally, and the most promising were assessed experimentally. Three MOFs with capacities surpassing that of IRMOF-20, the record-holder for balanced hydrogen capacity, are demonstrated: SNU-70, UMCM-9, and PCN-610/NU-100. Analysis of trends reveals the existence of a volumetric ceiling at ∼40 g H 2 L −1 . Surpassing this ceiling is proposed as a new capacity target for hydrogen adsorbents. Counter to earlier studies of total hydrogen uptake in MOFs, usable capacities in the highest-capacity materials are negatively correlated with density and volumetric surface area. Instead, capacity is maximized by increasing gravimetric surface area and porosity. This suggests that property/performance trends for total capacities may not translate to usable capacities.

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MOFs that exhibit a rare combination of high volumetric and gravimetric densities of stored H2are identified computationally and demonstrated experimentally.

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Porous adsorbents such as MOF-5 have low thermal conductivities which can limit the performance of adsorption-based hydrogen storage systems. To improve the thermal properties of these materials, we have prepared a series of high-density MOF-5 composites containing 0−10 wt % expanded natural graphite (ENG), which serves as a thermal conduction enhancer. The addition of 10 wt % ENG to MOF-5 and compaction to 0.5 g/ cm 3 was previously found to increase the thermal conductivity relative to neat MOF-5 of the same density by a factor of 5. In this study, detailed measurements of the hydrogen storage behavior of MOF-5/ENG composites between 77 and 295 K are reported. We find that MOF-5 pellets with 0 wt % ENG and a density of 0.5 g/cm 3 have a total volumetric hydrogen storage density at 77 K and 100 bar that is 23% larger than powder MOF-5 and 41% larger than cryo-compressed hydrogen. The addition of 10% ENG to 0.5 g/cm 3 MOF-5 pellets produces only a small decrease (6%) in the total volumetric hydrogen storage compared to neat MOF-5 pellets of equal density. The excess, absolute, total, and deliverable hydrogen storage amounts by the MOF-5 composites are compared for ENG additions of 0−10 wt % and pellet densities of 0.3−0.7 g/cm 3 . Three adsorption models (Unilan, Toth, Dubinin− Astakhov) are compared for their effectiveness in describing hydrogen adsorption isotherms of MOF-5 and MOF-5/ENG composites. The Unilan model provides the most accurate description of the experimental data, requiring only five temperatureinvariant parameters to accurately fit the data across a wide temperature range.

Metal-organic frameworks (MOFs) are an emerging class of microporous, crystalline materials with potential applications in the capture, storage, and separation of gases. Of the many known MOFs, MOF-5 has attracted considerable attention because of its ability to store gaseous fuels at low pressure with high densities. Nevertheless, MOF-5 and several other MOFs exhibit limited stability upon exposure to reactive species such as water. The present study quantifies the impact of humid air exposure on the properties of MOF-5 as a function of exposure time, humidity level, and morphology (i.e., powders vs pellets). Properties examined include hydrogen storage capacity, surface area, and crystallinity. Water adsorption/desorption isotherms are measured using a gravimetric technique; the first uptake exhibits a type V isotherm with a sudden increase in uptake at ∼50% relative humidity. For humidity levels below this threshold only minor degradation is observed for exposure times up to several hours, suggesting that MOF-5 is more stable than generally assumed under moderately humid conditions. In contrast, irreversible degradation occurs in a matter of minutes for exposures above the 50% threshold. Fourier transform infrared spectroscopy indicates that molecular and/or dissociated water is inserted into the skeletal framework after long exposure times. Densification into pellets can slow the degradation of MOF-5 significantly, and may present a pathway to enhance the stability of some MOFs.

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