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

2022 ◽  
Vol 8 (1) ◽  
pp. 5
Author(s):  
Jose A. Villajos

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.

2020 ◽  
Author(s):  
Diletta Morelli Venturi ◽  
Filippo Campana ◽  
Fabio Marmottini ◽  
Ferdinando Costantino ◽  
Luigi Vaccaro

<p>Zirconium based Metal-Organic Framework UiO-66 is to date considered one of the benchmark compound among stable MOFs and it has attracted a huge attention for its employment in many strategic applications. Large scale production of UiO-66 for industrial purposes requires the use of safe and green solvents, fulfilling the green chemistry principles and able to replace the use of <i>N,N</i>-Dimethyl-Formamide (DMF), which, despite its toxicity, is still considered the most efficient solvent for obtaining UiO-66 of high quality. Herein we report on a survey of about 40 different solvents with different polarity, boiling point and acidity, used for the laboratory scale synthesis of high quality UiO-66 crystals. The solvents were chosen according the European REACH Regulation 1907/2006 among those having low cost, low toxicity and fully biodegradable. Concerning MOF synthesis, the relevant parameters chosen for establishing the quality of the results obtained are the degree are the crystallinity, microporosity and specific surface area, yield and solvent recyclability. Taking into account also the chemical physical properties of all the solvents, a color code was assigned in order to give a final green assessment for the UiO-66 synthesis. Defectivity of the obtained products, the use of acidic modulators and the use of alternative Zr-salts have been also taken into consideration. Preliminary results lead to conclude that GVL (γ-valerolactone) is among the most promising solvents for replacing DMF in UiO-66 MOF synthesis. </p>


2020 ◽  
Author(s):  
Diletta Morelli Venturi ◽  
Filippo Campana ◽  
Fabio Marmottini ◽  
Ferdinando Costantino ◽  
Luigi Vaccaro

<p>Zirconium based Metal-Organic Framework UiO-66 is to date considered one of the benchmark compound among stable MOFs and it has attracted a huge attention for its employment in many strategic applications. Large scale production of UiO-66 for industrial purposes requires the use of safe and green solvents, fulfilling the green chemistry principles and able to replace the use of <i>N,N</i>-Dimethyl-Formamide (DMF), which, despite its toxicity, is still considered the most efficient solvent for obtaining UiO-66 of high quality. Herein we report on a survey of about 40 different solvents with different polarity, boiling point and acidity, used for the laboratory scale synthesis of high quality UiO-66 crystals. The solvents were chosen according the European REACH Regulation 1907/2006 among those having low cost, low toxicity and fully biodegradable. Concerning MOF synthesis, the relevant parameters chosen for establishing the quality of the results obtained are the degree are the crystallinity, microporosity and specific surface area, yield and solvent recyclability. Taking into account also the chemical physical properties of all the solvents, a color code was assigned in order to give a final green assessment for the UiO-66 synthesis. Defectivity of the obtained products, the use of acidic modulators and the use of alternative Zr-salts have been also taken into consideration. Preliminary results lead to conclude that GVL (γ-valerolactone) is among the most promising solvents for replacing DMF in UiO-66 MOF synthesis. </p>


2017 ◽  
Vol 201 ◽  
pp. 63-70 ◽  
Author(s):  
Nian Zhao ◽  
Ping Li ◽  
Xin Mu ◽  
Chuanfang Liu ◽  
Fuxing Sun ◽  
...  

A novel ultra-stable metal–organic framework, MCIF-1, [Cu2(DCI)2](MeCN), based on dicyanoimidazole and Cu(i), has been synthesized at room temperature successfully. MCIF-1 shows excellent water stability and can retain crystallinity after soaking in water for about one week. In addition, MCIF-1 also shows exceptional resistance under both acidic and basic conditions within a large pH range from 0 to 13.5. What is more, after modifying the synthesis procedure slightly, we can produce this material in a large scale during a very short time. Mild synthesis conditions, excellent stability and ease of large scale production give MCIF-1 great potential for practical use.


2016 ◽  
Vol 1 (4) ◽  
pp. 352-360 ◽  
Author(s):  
Peter W. Dunne ◽  
Edward Lester ◽  
Richard I. Walton

Continuous flow synthesis offers potential for large-scale production of metal–organic frameworks with control of composition and microstructure for practical applications.


2021 ◽  
Vol 303 ◽  
pp. 122547
Author(s):  
Tong Gao ◽  
Hui-Juan Tang ◽  
Shu-Yi Zhang ◽  
Jian-Wei Cao ◽  
Yi-Nong Wu ◽  
...  

2013 ◽  
Vol 38 (29) ◽  
pp. 13000-13010 ◽  
Author(s):  
Jinsheng Xiao ◽  
Min Hu ◽  
Pierre Bénard ◽  
Richard Chahine

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