Activated Carbon Fibre Monoliths for Hydrogen Storage

Porous adsorbents are currently investigated for hydrogen storage application. From a practical point of view, in addition to high porosity developments, high material densities are required, in order to confine as much material as possible in a tank device. In this study, we use different measured sample densities (tap, packing, compacted and monolith) for analyzing the hydrogen adsorption behavior of activated carbon fibres (ACFs) and activated carbon nanofibres (ACNFs) which were prepared by KOH and CO2 activations, respectively. Hydrogen adsorption isotherms are measured for all of the adsorbents at room temperature and under high pressures (up to 20 MPa). The obtained results confirm that (i) gravimetric H2 adsorption is directly related to the porosity of the adsorbent, (ii) volumetric H2 adsorption depends on the adsorbent porosity and importantly also on the material density, (iii) the density of the adsorbent can be improved by packing the original adsorbents under mechanical pressure or synthesizing monoliths from them, (iv) both ways (packing under pressure or preparing monoliths) considerably improve the storage capacity of the starting adsorbents, and (v) the preparation of monoliths, in addition to avoid engineering constrains of packing under mechanical pressure, has the advantage of providing high mechanical resistance and easy handling of the adsorbent

Sorbent design for CO2 capture under different flue gas conditions

CO2 capture by solid sorbents is a physisorption process in which the gas molecules are adsorbed in a different porosity range, depending on the temperature and pressure of the capture conditions. Accordingly, CO2 capture capacities can be enhanced if the sorbent has a proper porosity development and a suitable pore size distribution. Thus, the main objective of this work is to maximize the CO2 capture capacity at ambient temperature, elucidating which is the most suitable porosity that the adsorbent has to have as a function of the emission source conditions. In order to do so, different activated carbons have been selected and their CO2 capture capacities have been measured. The obtained results show that for low CO2 pressures (e.g., conditions similar to post-combustion processes) the sorbent should have the maximum possible volume of micropores smaller than 0.7 nm. However, the sorbent requires the maximum possible total micropore volume when the capture is performed at high pressures (e.g., conditions similar to oxy-combustion or pre-combustion processes). Finally, this study also analyzes the important influence that the sorbent density has on the CO2 capture capacity, since the adsorbent will be confined in a bed with a restricted volume.The authors thank the Generalitat Valenciana and FEDER (project PROMETEO/2009/047) for financial support

Gas Storage Scale-up at Room Temperature on High Density Carbon Materials

In relation to the current interest on gas storage demand for environmental applications (e.g., gas transportation, and carbon dioxide capture) and for energy purposes (e.g., methane and hydrogen), high pressure adsorption (physisorption) on highly porous sorbents has become an attractive option. Considering that for high pressure adsorption, the sorbent requires both, high porosity and high density, the present paper investigates gas storage enhancement on selected carbon adsorbents, both on a gravimetric and on a volumetric basis. Results on carbon dioxide, methane, and hydrogen adsorption at room temperature (i.e., supercritical and subcritical gases) are reported. From the obtained results, the importance of both parameters (porosity and density) of the adsorbents is confirmed. Hence, the densest of the different carbon materials used is selected to study a scale-up gas storage system, with a 2.5 l cylinder tank containing 2.64 kg of adsorbent. The scale-up results are in agreement with the laboratory scale ones and highlight the importance of the adsorbent density for volumetric storage performances, reaching, at 20 bar and at RT, 376 g l-1, 104 g l-1, and 2.4 g l-1 for CO2, CH4,and H2, respectively.Generalitat Valenciana and FEDER (project PROMETEO/2009/047)

A comparison between oxidation of activated carbon by electrochemical and chemical treatments

The anodic oxidation of a granular activated carbon (GAC) in NaCl solution has been studied. The influence of the electrocatalyst-anode material, applied current and time of treatment on both the surface chemistry and porous texture properties of the GAC has been analyzed. For comparison purposes, the same GAC has been treated with three of the classical chemical oxidants: HNO 3, H 2O 2 and (NH 4) 2S 2O 8 at different concentrations and for different times. Results show that the anodic treatment in NaCl causes a remarkable oxidation of the AC without modifying significantly its textural properties. TPD profiles and the linear dependence of the amount of CO- and CO 2-evolution against the oxidation level denotes that surface oxygen groups of similar nature and composition are formed anodically, regardless of the anode material. The achieved oxidation degree depends on the different ability of each anode for the electrochemical generation of highly oxidizing chlorine species, and it increases progressively with the applied current and the time of treatment. In general, for similar treatment times, the anodic treatment in NaCl can produce oxidation degrees much higher than the chemical treatment with (NH 4) 2S 2O 8, which has been found to be the most oxidative chemical studied in this work.Financial support by the Ministerio de Ciencia e Innovacion (MAT2010-15273 and CTQ2009-10813) and Generalitat Valenciana and FEDER (PROMETEO/2009/047) projects are gratefully acknowledged.Berenguer, R.; Marco-Lozar, JP.; Quijada Tomás, C.; Cazorla-Amoros, D.; Morallón, E. (2012). A comparison between oxidation of activated carbon by electrochemical and chemical treatments. Carbon. 50(3):1123-1134. https://doi.org/10.1016/j.carbon.2011.10.025S1123113450

Comparison among Chemical, Thermal, and Electrochemical Regeneration of Phenol-Saturated Activated Carbon

The regeneration of phenol-saturated activated carbon (AC) by chemical, thermal, and electrochemical techniques has been studied and compared in this work. The influence of the solute (NaOH) concentration and the temperature on the conventional chemical and thermal regenerations, respectively, has been analyzed and compared to the optimal results achieved for the electrochemical method. Comparisons are based on the analysis of the remaining products after regeneration, the regeneration efficiency (RE), and the recovery of the textural properties of a commercial phenol-saturated granular AC. Results show that very low-porosity recoveries are achieved by chemical regeneration, independent of the NaOH concentration, and the optimal REs are 20% lower than those obtained by the thermal and electrochemical ones. REs obtained by thermal treatment in an inert atmosphere increase with the temperature up to 750 °C, reaching the highest REs (80−86%) and porosity recoveries at T > 600 °C. The cathodic regeneration in the NaOH medium in an undivided cell, where phenolate desorption is favored and surface blockage is minimized, yields similar RE values (80−85%) and slightly higher porosity than those obtained by thermal treatment. Temperature-programmed desorption (TPD) experiments show that, whereas phenol is almost completely removed electrochemically after 3 h, a temperature of at least 450−600 °C is required to achieve similar results by thermal regeneration.The authors thank the Ministerio de Ciencia e Innovación (MICINN), FEDER and PlanE (Projects CTQ2009-10813, MAT2007-60621 and PLE2009-0021) and GV (ACOMP/2009/174 and PROMETEO/2009/047) for financial support

Tailoring the porosity of chemically activated hydrothermal carbons: Influence of the precursor and hydrothermal carbonization temperature

Advanced porous materials with tailored porosity (extremely high development of microporosity together with a narrow micropore size distribution (MPSD)) are required in energy and environmental related applications. Lignocellulosic biomass derived HTC carbons are good precursors for the synthesis of activated carbons (ACs) via KOH chemical activation. However, more research is needed in order to tailor the microporosity for those specific applications. In the present work, the influence of the precursor and HTC temperature on the porous properties of the resulting ACs is analyzed, remarking that, regardless of the precursor, highly microporous ACs could be generated. The HTC temperature was found to be an extremely influential parameter affecting the porosity development and the MPSD of the ACs. Tuning of the MPSD of the ACs was achieved by modification of the HTC temperature. Promising preliminary results in gas storage (i.e. CO2 capture and high pressure CH4 storage) were obtained with these materials, showing the effectiveness of this synthesis strategy in converting a low value lignocellulosic biomass into a functional carbon material with high performance in gas storage applications.MMT and CF would like to thank the Max-Planck Society for financial support. DLC, DST, JPML and DCA would like to thank the Spanish MINECO, Generalitat Valenciana and FEDER (Projects CTQ2012-31762 and PROMETEO/2009/047) for financial support. DST. thanks MICCIN (BES-2010-035238)

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

Scale-up activation of carbon fibres for hydrogen storage

In a previous study, we investigated, at a laboratory scale, the chemical activation of two different carbon fibres (CF), their porosity characterization, and their optimization for hydrogen storage [1]. In the present work, this study is extended to: (i) a larger range of KOH activated carbon fibres, (ii) a larger range of hydrogen adsorption measurements at different temperatures and pressures (i.e. at room temperature, up to 20 MPa, and at 77 K, up to 4 MPa), and (iii) a scaling-up activation approach in which the obtained activated carbon fibres (ACF) are compared with those from laboratory-scale activation. The prepared samples cover a large range of porosities, which is found to govern their ability for hydrogen adsorption. The hydrogen uptake capacities of all the prepared samples have been analysed both in volumetric and in gravimetric bases. Thus, maximum adsorption capacities of around 5 wt% are obtained at 77 K, and 1.1 wt% at room temperature, respectively. The packing densities of the materials have been measured, turning out to play an important role in order to estimate the total storage capacity of a tank volume. Maximum values of 17.4 g/l at 298 K, and 38.6 g/l at 77 K were obtained.Osaka Gas Co., Ltd. supplied the two precursor materials. Financial help was received from the European Union (Marie Curie Research Training Network-HyTRAIN-Project reference: 512443), MEC (ENE2005-23824-E/CON), the Generalitat Valenciana (ACOMP06/089 and PROMETEO/2009/047), as well as MEC-CTQ2006-08958/PPQ

Material demands for storage technologies in a hydrogen economy

A hydrogen economy is needed, in order to resolve current environmental and energy-related problems. For the introduction of hydrogen as an important energy vector, sophisticated materials are required. This paper provides a brief overview of the subject, with a focus on hydrogen storage technologies for mobile applications. The unique properties of hydrogen are addressed, from which its advantages and challenges can be derived. Different hydrogen storage technologies are described and evaluated, including compression, liquefaction, and metal hydrides, as well as porous materials. This latter class of materials is outlined in more detail, explaining the physisorption interaction which leads to the adsorption of hydrogen molecules and discussing the material characteristics which are required for hydrogen storage application. Finally, a short survey of different porous materials is given which are currently investigated for hydrogen storage, including zeolites, metal organic frameworks (MOFs), covalent organic frameworks (COFs), porous polymers, aerogels, boron nitride materials, and activated carbon materials.Generalitat Valenciana and FEDER (Project PROMETEO/2009/047)

Biodiesel production by acid catalysis with heteropolyacids supported on activated carbon fibers

Different catalysts, based on heteropolyacids supported on activated carbon fibers, have been prepared for palmitic acid esterification reaction. The influence of the catalyst (heteropolyacid) and the support on the catalytic activity have been analyzed. The results prove that an adequate combination of both is required to achieve the most suitable catalysts. Regarding to the heteropolyacid, phosphomolybdic acid seems to be the most suitable appropriate taking into account its lowest leaching. About the support, it must show an optimum microporosity, which must be wide enough to allow the entrance and exit of the reagents and products but not too wide in order to avoid the leaching of the catalyst. In addition, both decreasing of the catalytic activity and its recovery over several cycles have been analyzed.The authors thank the Generalitat Valenciana and FEDER(PROMETEO/2009/047), and MICINN and Plan E (CTQ2012-31762)for the financial support