Establishing ZIF-8 as a reference material for hydrogen cryoadsorption: An interlaboratory study

Hydrogen storage by cryoadsorption on porous materials has the advantages of low material cost, safety, fast kinetics, and high cyclic stability. The further development of this technology requires reliable data on the H2 uptake of the adsorbents, however, even for activated carbons the values between different laboratories show sometimes large discrepancies. So far no reference material for hydrogen cryoadsorption is available. The metal-organic framework ZIF-8 is an ideal material possessing high thermal, chemical, and mechanical stability that reduces degradation during handling and activation. Here, we distributed ZIF-8 pellets synthesized by extrusion to 9 laboratories equipped with 15 different experimental setups including gravimetric and volumetric analyzers. The gravimetric H2 uptake of the pellets was measured at 77 K and up to 100 bar showing a high reproducibility between the different laboratories, with a small relative standard deviation of 3–4 % between pressures of 10–100 bar. The effect of operating variables like the amount of sample or analysis temperature was evaluated, remarking the calibration of devices and other correction procedures as the most significant deviation sources. Overall, the reproducible hydrogen cryoadsorption measurements indicate the robustness of the ZIF-8 pellets, which we want to propose as a reference material.M. Maiwald, J. A. Villajos, R. Balderas and M. Hirscher acknowledge the EMPIR programme from the European Union's Horizon 2020 research and innovation programme for funding. F. Cuevas and F. Couturas acknowledge support from France 2030 program under project ANR-22-PEHY-0007. D. Cazorla and A. Berenguer-Murcia thank the support by PID2021-123079OB-I00 project funded by MCIN/AEI/10.13039/501100011033, and “ERDF A way of making Europe”. K. N. Heinselman, S. Shulda and P. A. Parilla acknowledge the support from the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding provided by U.S. Department of Energy Office of Energy Efficiency and Renewable Energy Hydrogen and Fuel Cell Technology Office through the HyMARC Energy Materials Network

Experimental Volumetric Hydrogen Uptake Determination at 77 K of Commercially Available Metal-Organic Framework Materials

Storage is still limiting the implementation of hydrogen as an energy carrier to integrate the intermittent operation of renewable energy sources. Among different solutions to the currently used compressed or liquified hydrogen systems, physical adsorption at cryogenic temperature in porous materials is an attractive alternative due to its fast and reversible operation and the resulting reduction in storage pressure. The feasibility of cryoadsorption for hydrogen storage depends mainly on the performance of the used materials for the specific application, where metal-organic frameworks or MOFs are remarkable candidates. In this work, gravimetric and volumetric hydrogen uptakes at 77 K and up to 100 bar of commercially available MOFs were measured since these materials are made from relatively cheap and accessible building blocks. These materials also show relatively high porous properties and are currently near to large-scale production. The measuring device was calibrated at different room temperatures to calculate an average correction factor and standard deviation so that the correction deviation is included in the measurement error for better comparability with different measurements. The influence of measurement conditions was also studied, concluding that the available adsorbing area of material and the occupied volume of the sample are the most critical factors for a reproducible measurement, apart from the samples’ preparation before measurement. Finally, the actual volumetric storage density of the used powders was calculated by directly measuring their volume in the analysis cell, comparing that value with the maximum volumetric uptake considering the measured density of crystals. From this selection of commercial MOFs, the materials HKUST-1, PCN-250(Fe), MOF-177, and MOF-5 show true potential to fulfill a volumetric requirement of 40 g·L−1 on a material basis for hydrogen storage systems without further packing of the powders

ZIF‑8 Pellets as a Robust Material for Hydrogen Cryo-Adsorption Tanks

Cryoadsorption on the inner surface of porous materials is a promising solution for safe, fast, and reversible hydrogen storage. Within the class of highly porous metal–organic frameworks, zeolitic imidazolate frameworks (ZIFs) show high thermal, chemical, and mechanical stability. In this study, we selected ZIF-8 synthesized mechanochemically by twin-screw extrusion as powder and pellets. The hydrogen storage capacity at 77 K and up to 100 bar has been analyzed in two laboratories applying three different measurement setups showing a high reproducibility. Pelletizing ZIF-8 increases the packing density close to the corresponding value for a single crystal without loss of porosity, resulting in an improved volumetric hydrogen storage capacity close to the upper limit for a single crystal. The high volumetric uptake combined with a low and constant heat of adsorption provides ca. 31 g of usable hydrogen per liter of pellet assuming a temperature–pressure swing adsorption process between 77 K – 100 bar and 117 K – 5 bar. Cycling experiments do not indicate any degradation in storage capacity. The excellent stability during preparation, handling, and operation of ZIF-8 pellets demonstrates its potential as a robust adsorbent material for technical application in pilot- and full-scale adsorption vessel prototypes

Lighting Up Industrial Mechanochemistry: Real-Time In Situ Monitoring of Reactive Extrusion Using Energy-Dispersive X-Ray Diffraction

Mechanochemistry is an environmentally friendly synthetic approach enabling the sustainable production of a wide range of chemicals while reducing or eliminating the need for solvents. Reactive extrusion aims to move mechanochemistry from its conventional gram-scale batch reactions, typically performed in laboratory ball mills, to a continuous large-scale process. Meeting this challenge requires the use of in situ monitoring techniques for gaining insights into reactive extrusion and its underlying processes. While the effectiveness of in situ Raman spectroscopy in providing molecular-level information has been demonstrated, our study uses energy-dispersive X-ray diffraction to monitor reactive extrusion in real-time at the crystalline level

Optimizing the Green Synthesis of ZIF‑8 by Reactive Extrusion Using <i>In Situ</i> Raman Spectroscopy

We report the scale-up of a batch solid synthesis of zeolitic imidazolate framework-8 (ZIF-8) for reactive extrusion. The crystalline product forms in the extruder directly under the mixture of solid 2-methylimidazole and basic zinc carbonate in the presence of a catalytic amount of liquid. The process parameters such as temperature, liquid type, feeding rate, and linker excess were optimized using the setup specifically designed for in situ Raman spectroscopy. Highly crystalline ZIF-8 with a Brunauer–Emmett–Teller (BET) surface area of 1816 m2 g–1 was quantitatively prepared at mild temperature using a catalytic amount of ethanol and a small excess of the linker. Finally, we developed a simple and comprehensive approach to evaluating the environmental friendliness and scalability of metal–organic framework (MOF) syntheses in view of their large-scale production

Natural Enrichment of Trace Elements in Surface Horizons of Calcareous Soils (La Mancha, Spain)

The study of five soil profiles developed on carbonatic sediments of Tertiary Miocene origin has been carried out. The topography of the area was basically flat and the traditional uses of the soils are the cultivation of dry cereals and grapevine. The geochemical characterization of the aforementioned profiles involves a study of the contents of major and trace elements among other pedologic aspects (texture, pH, organic matter, etc.). The results of this study also indicate a superficial enrichment of trace elements due to the leaching of Ca and moderate biological and anthropic activity. We can consider strontium, Sr, as the trace element that characterizes these limy soils (435 mg/kg average content in total soil and 708 mg/kg in the original rock). These contents are similar to the average value in Castilla-La Mancha of 380 mg/kg and are higher than the average in world soils of about 200 mg/kg. High levels of dangerous or pollutant elements (Cd, Hg, Pb, Cu, Zn, or Ni) were not detected. The majority of trace element anomalies are related to calcareous material and the leaching of calcium carbonate (Ca), while the influence of the anthropogenic factor is secondary. Soil quality does not indicate toxicity although surficial enrichment suggests a weak threat from consuming crops

Establishing ZIF-8 as a reference material for hydrogen cryoadsorption: An interlaboratory study.

Publication status: PublishedHydrogen storage by cryoadsorption on porous materials has the advantages of low material cost, safety, fast kinetics, and high cyclic stability. The further development of this technology requires reliable data on the H2 uptake of the adsorbents, however, even for activated carbons the values between different laboratories show sometimes large discrepancies. So far no reference material for hydrogen cryoadsorption is available. The metal-organic framework ZIF-8 is an ideal material possessing high thermal, chemical, and mechanical stability that reduces degradation during handling and activation. Here, we distributed ZIF-8 pellets synthesized by extrusion to 9 laboratories equipped with 15 different experimental setups including gravimetric and volumetric analyzers. The gravimetric H2 uptake of the pellets was measured at 77 K and up to 100 bar showing a high reproducibility between the different laboratories, with a small relative standard deviation of 3-4 % between pressures of 10-100 bar. The effect of operating variables like the amount of sample or analysis temperature was evaluated, remarking the calibration of devices and other correction procedures as the most significant deviation sources. Overall, the reproducible hydrogen cryoadsorption measurements indicate the robustness of the ZIF-8 pellets, which we want to propose as a reference material