Hydrogen uptake of high surface area-activated carbons doped with nitrogen

Three activated carbons (ACs) having apparent surface areas higher than 2500 m²/g were doped with nitrogen by treatment with urea at 623 K under air flow. Nitrogen contents as high as 15.1 wt.% were obtained, but resulting in decreased surface areas and pore volumes. Hydrogen storage capacities of ACs before and after nitrogen doping were measured at 77 K and up to 8 MPa. After doping, the hydrogen uptake was lower due to the corresponding decrease of surface area. Statistical, ANOVA, analysis of the relevancy of surface area and nitrogen content on hydrogen storage at 77 K was carried out, taking into account our data and those data available in the open literature. We concluded that surface area controls hydrogen adsorption and nitrogen content is not a relevant parameter.     

Microstructure regulation of super activated carbon from biomass source corncob with enhanced hydrogen uptake

A series of super activated carbon have been prepared by potassium hydroxide activation of corncob. The as-obtained samples were characterized by SEM, TEM and N₂-sorption. The results show morphologies and textural of activated carbon are highly depended on the activation temperature, heating rate, whereas the activation time is not a key factor. Morphologies and porous structure of activated carbons can be regulated by adjusting preparation parameters. A super activated carbon with BET surface area of 3530 m²/g and total pore volume of 1.94 cm³/g is obtained. However, the other activated carbon with smaller pore size exhibited the highest hydrogen uptake capacities exceeding 2.85 wt% at −196 °C and 1.0 bar, whose BET surface area is only 2988 m²/g. The correlation investigations show the micropore volume between 0.65 nm and 1.5 nm can be more important than BET surface area and total pore volume for hydrogen uptakes at −196 °C. The present results indicate that the corncob-derived activated carbons can be promising materials for hydrogen storage.     

Adsorption and compression contributions to hydrogen storage in activated anthracites

We prepared activated carbons (ACs) that are among the best adsorbents for hydrogen storage. These ACs were prepared from anthracites and have surface areas (S_BET) as high as 2772 m² g⁻¹. Anthracites activated with KOH presented the highest adsorption capacities with a maximum of 5.3 wt.% at 77 K and 4 MPa. Non-linearity between hydrogen uptake at 77 K and pore texture was confirmed, as soon as their S_BET exceeded the theoretical limiting value of (geometrical) surface area, i.e., S_BET > 2630 m² g⁻¹. We separated adsorption and compression contributions to total hydrogen storage. The amount of hydrogen stored is significantly increased by adsorption only at moderate pressure: 3 MPa and 0.15 MPa at 298 and 77 K, respectively. Hydrogen adsorption on ACs at high pressure, above 30 MPa at 298 K and 8 MPa at 77 K, has not interest because more gas can be stored by simply compression in the same tank volume.     

Investigation of hydrogen storage capacity of multi-walled carbon nanotubes deposited with Pd or V

This work presents the synthesis and characterization of multi-walled carbon nanotubes (multi-walled CNTs) deposited with Pd or V and their hydrogen storage capacity measured by Sievert's volumetric apparatus. The CNTs were grown by the CVD method using LPG and LaNi₅ as the carbon source and catalyst, respectively. Pd was impregnated on the CNTs by the reflux method with hydrogen gas as a reducing agent, while V was embedded on the CNTs by the vapor deposition method. The average metal particle size deposited on the CNTs was around 5.8 nm for Pd and 3.6 nm for V. Hydrogen adsorption experiments were performed at room temperature and at −196 °C under a hydrogen pressure of 65 bar. At −196 °C, the treated CNTs had a maximum hydrogen uptake of 1.21 wt%, while the CNTs deposited with Pd (Pd-CNTs) and CNTs deposited with V (V-CNTs) possessed lower surface areas, inducing lower hydrogen adsorption capacities of 0.37 and 0.4 wt%, respectively. For hydrogen sorption at room temperature, the CNTs decorated with the metal nanoparticles had a higher hydrogen uptake compared to the treated CNTs. Hydrogen adsorption capacity was 0.125 and 0.1 wt% for the Pd-CNTs and V-CNTs, respectively, while the hydrogen uptake of the treated CNTs was <0.01 wt%. For the second cycle, only half of the first hydrogen uptake was obtained, and this was attributed to the re-crystallization of the defect sites on the carbon substrate after the first hydrogen desorption.     

Activated carbons doped with Pd nanoparticles for hydrogen storage

Three activated carbons (ACs) having apparent surface areas ranging from 2450 to 3200 m²/g were doped with Pd nanoparticles at different levels within the range 1.3–10.0 wt.%. Excess hydrogen storage capacities were measured at 77 and 298 K at pressures up to 8 MPa. We show that hydrogen storage at 298 K depends on Pd content at pressures up to 2–3 MPa, below which the stored amount is low (<0.2 wt.%). At higher pressures, the micropore volume controls H₂ storage capacity. At 77 K, Pd doping has a negative effect on hydrogen storage whatever the pressure considered. From N₂ adsorption at 77 K, TPR, XRD, TEM, and H₂ chemisorption studies, we concluded that: (i) Pd particles remained mainly decorating the outer surface of the ACs; (ii) increasing Pd content produced an increase of the metal particle size; (iii) ACs with higher surface area produced smaller metallic nanoparticles at a given Pd content.     

Impact of synthesis conditions of KOH activated carbons on their hydrogen storage capacities

39 activated carbons (ACs) were prepared by KOH activation of anthracite, using weight ratios KOH/anthracite (W) ranging from 1.5 to 7, activation temperatures (T) from 973 to 1073 K, and heating rates (Hr) from 1 to 5 K min⁻¹. ACs with high apparent surface areas (>3400 m² g⁻¹), high micropore volumes (>1 cm³ g⁻¹) and high hydrogen storage capacities (up to 6.6 wt. %) were obtained. A statistical study was carried out to clarify the impact of synthesis conditions on hydrogen storage capacities of the resultant ACs. Analysis of variance (ANOVA) showed that both W and T have a significant impact on hydrogen storage capacity, whereas Hr has not. A quadratic model was used to correlate W², W, T² and T to hydrogen storage capacities. The model adequately evaluated the impact of synthesis conditions on hydrogen storage capacities of the resultant ACs.     

Study of hydrogen physisorption on nanoporous carbon materials of different origin

Hydrogen adsorption capabilities of different nanoporous carbon, i.e. amorphous carbons obtained by chemical activation (with KOH) of a sucrose-derived char previously ground by ball milling and carbon replicas of NH₄-Y and mesocellular silica foam (MSU-F) inorganic templates, were measured and correlated to their porous properties. The porous texture of the prepared carbon materials was studied by means of N₂ and CO₂ adsorption isotherms measured at −196 °C and 0 °C, respectively. Comparison with nanoporous carbons obtained without pre-grinding the sucrose-derived char [12] shows that the ball milling procedure favours the formation of highly microporous carbon materials even at low KOH loadings, having a beneficial effect of the interaction between the char particles and the activating agent. Hydrogen adsorption isotherms at −196 °C were measured in the 0.0-1.1 MPa pressure range, and a maximum hydrogen adsorption capacity of 3.4 wt.% was obtained for the amorphous carbon prepared by activation at 900 °C with a KOH/char weight ratio of 2. Finally, a linear dependence was found between the maximum hydrogen uptake at 1.1 MPa and the samples microporous volume, confirming previous results obtained at −196 °C and sub-atmospheric pressure [12].     

Thermochemical method for controlling pore structure to enhance hydrogen storage capacity of biochar

Developing new carbon-based hydrogen storage materials can significantly promote solid-state hydrogen storage technology. Biochar with high hydrogen storage capacity can be prepared by KOH melt activation, which has a high proportion of micropores (96.56%) compared with the porous carbon in the existing literature. Its specific surface area and pore volume are 2801.88 m²/g and 1.44 cm³/g, respectively. The size of the nanopores is affected by the activation ratio, but the temperature has little effect at the low activation ratio. SEM results show that the KOH activation process gradually shifts from the biochar's inside to the outside. A low KOH/char ratio (less than 2:1) can promote the formation of small aromatic rings. Due to its high specific surface area and microporosity, the absolute adsorption capacity of hydrogen in biochar is 2.53 wt% at −196 °C and 1 bar, rising to 5.32 wt% at 50 bar. The hydrogen adsorption process conforms to the Langmuir model. Microporous, mesoporous, and macroporous exhibit different hydrogen adsorption characteristics in various pressure ranges. However, ultramicroporous (<0.7 nm) always plays a decisive role in the hydrogen storage of biochar.     

A simple method for the production of highly ordered porous carbon materials with increased hydrogen uptake capacities

The synthesis, characterization and hydrogen uptake of porous carbons generated by heat treatment was investigated using various zeolites and mesoporous silicas as hard templates. The effect of heat treatment on the structural order, textural properties and hydrogen uptake capacities of porous carbons templated from the model zeolite EMC-2 in a temperature range of 600–800 °C during chemical vapour deposition were studied in details. The heat treatment improved the structural order of replicated microporous carbons, significantly increased both total and microporous surface area and pore volume, and remarkably increased the hydrogen uptake capacity. The optimized heat treatment conditions were at 900 °C for 3 h. The heat treatment at high temperatures was found to be a simple and general approach to synthesize well-ordered microporous carbons from different zeolite templates, using various carbon precursors and through different synthesis methods. The microporous carbons possessed a high surface area and pore volume with increased microporosity and therefore exhibited improved hydrogen storage capacities up to 5.85 wt% at 20 bar and −196 °C. The heat treatment, however, has no obvious effect on the textural properties and hydrogen uptake capacities for mesoporous carbons templated from mesoporous silicas.     

Hydrogen storage in ordered and disordered phenylene-bridged mesoporous organosilicas

Novel hexagonal Periodic Mesoporous Organosilicas (PMOs) and Disordered Mesoporous Organosilicas (DMOs) were synthesized by hydrolysis of 1,4-bis(trialkoxylsilyl) benzene precursor in alkaline aqueous solutions of different alkyl-trimethyl ammonium cations and evaluated for their hydrogen storage capacity. The PMO materials exhibit regular hexagonal pore arrangement and specific surface area between 640 and 782 m² g⁻¹ whereas the DMO materials have specific surface area that lies between 650 and 910 m² g⁻¹. The storage capacity of the materials is discussed in terms of number of molecules per surface unit. The materials exhibit a reversible hydrogen excess surface adsorption capacity up to 2.10 wt% at 6 MPa and 77 K. DFT calculations were performed to define the binding strength of hydrogen with the pore walls indicated an interaction energy value of −0.55 Kcal mol⁻¹, higher than the interaction energy value of hydrogen with a single benzene or a benzene incorporated in the IRMOR-1 walls. Grand Canonical Monte Carlo (GCMC) simulations showed that no hydrogen molecule can be inserted inside the wall structure of the materials.     

Application of the modified Dubinin-Astakhov equation for a better understanding of high-pressure hydrogen adsorption on activated carbons

Hydrogen storage in activated carbons (ACs) has proven to be a realistic alternative to compression and liquefaction. Adsorption capacities up to 5.8 wt% have indeed been obtained. The amount of adsorbed hydrogen depends on the textural properties of ACs, such as specific surface area and total pore volume. The modified Dubinin-Astakhov (MDA) equation proved to be a good analytical tool for describing hydrogen adsorption in a wide range of pressures and temperatures and for several adsorbents. The parameters of this model have been found to be somehow related to the textural properties of the adsorbent. Thus, we applied this model to understand better hydrogen adsorption on ACs over a wide range of pressures in relation to the textural properties of the ACs.We applied the MDA equation to evaluate also the isosteric heat of hydrogen adsorption, which was found to be in the range of 5–9 kJ mol⁻¹. We compared the results obtained by applying the MDA equation with those obtained by both the sorption isosteric method and the Sips equation. This allowed finding the temperature dependence of the isosteric heat of adsorption, as well as its variation with respect to the textural properties of the ACs.     

Effect of platinum doping of activated carbon on hydrogen storage behaviors of metal-organic frameworks-5

In this work, we prepared platinum doped on activated carbons/metal-organic frameworks-5 hybrid composites (Pt-ACs-MOF-5) to obtain a high hydrogen storage capacity. The surface functional groups and surface charges were confirmed by Fourier transfer infrared spectroscopy (FT-IR) and zeta-potential measurement, respectively. The microstructures were characterized by X-ray diffraction (XRD). The sizes and morphological structures were also evaluated using a scanning electron microscopy (SEM). The pore structure and specific surface area were analyzed by N₂/77 K adsorption/desorption isotherms. The hydrogen storage capacity was studied by BEL-HP at 298 K and 100 bar. The results revealed that the hydrogen storage capacity of the Pt-ACs-MOF-5 was 2.3 wt.% at 298 K and 100 bar, which is remarkably enhanced by a factor of above five times and above three times compared with raw ACs and MOF-5, respectively. In conclusion, it was confirmed that Pt particles played a major role in improving the hydrogen storage capacity; MOF-5 would be a significantly encouraging material for a hydrogen storage medium as a receptor.     

Development of exfoliated layered stannosilicate for hydrogen adsorption

The use of hydrogen as an energy vector leads to the development of materials with high hydrogen adsorption capacity. In this work, a new layered stannosilicate, UZAR-S3, is synthesized and delaminated, producing UZAR-S4. UZAR-S3, with the empirical formula Na₄SnSi₅O₁₄·3.5H₂O and lamellar morphology, is a layered stannosilicate built from SnO₆ and SiO₄ polyhedra. The delamination process used here comprises three stages: protonation with acetic acid, swelling with nonylamine and the delamination itself with an HCl/H₂O/ethanol solution. UZAR-S4 is composed of sheets a few nanometers thick with a high aspect ratio and a surface area of 236 m²/g, twenty times higher than that of UZAR-S3. At −196 °C for UZAR-S4, H₂ adsorption reached remarkable values of 3.7 and 4.2 wt% for 10 and 40 bar, respectively, the latter value giving a high volumetric H₂ storage capacity of 26.2 g of H₂/L.     

Hydrogen storage in Co-and Zn-based metal-organic frameworks at ambient temperature

Hydrogen adsorption properties of some Co-and Zn-based Metal-Organic Framework (MOF) materials were studied at near ambient temperatures. Maximal hydrogen storage capacity of 0.75 wt% was found for a Zn-based material at 175 Bar hydrogen pressure and T = −4 °C. Hydrogen adsorption correlated linearly with BET surface area and strongly depends on temperature. Relatively low structural stability of some MOF's results in framework collapse during degassing and hydrogen adsorption measurements.     

Volumetric hydrogen adsorption capacity of densified MIL-101 monoliths

The hydrogen adsorption isotherms of MIL-101 compressed pellets at 77.3 K are reported. The specific surface area and micropore volume decrease rather sharply when the pellet density approaches the crystal density. Optimum volumetric storage capacity of 40 g L⁻¹ is obtained for monoliths of remarkable mechanical integrity. The X-ray diffraction patterns do not exhibit notable changes with compression up to densities close to the crystal density. However, the infrared spectra show significant modification of the band structure in the range of vibration frequencies characteristic to the carboxylate and phenylene groups, due to the pressure-induced changes in the coordination environment of the metal, close to the adsorption sites. The compression effect on hydrogen adsorption can be correlated with the changes in the nitrogen adsorption isotherms. The results are discussed and compared with the literature results on volumetric hydrogen storage capacity of MOF-5 and MOF-177 monoliths.     

Hydrogen storage properties of highly cross-linked polymers derived from chlorinated polypropylene and polyethylenimine

Highly cross-linked polymer derived from chlorinated polypropylene (CPP) grafted with polyethylenimine (PEI) was synthesized by hydrothermal amination reaction. The influence of different reaction conditions on the structure and properties of highly cross-linked polymer was investigated. The structures of the polymers named CPP-g-PEI were characterized by Fourier transform infrared (FT-IR) spectroscopy, elemental analysis (EA), ¹³C solid-state NMR (¹³C NMR), thermogravimetric analysis (TG), scanning electron microscopy (SEM), transmission electron microscope (TEM), powder X-ray diffraction (PXRD) and nitrogen sorption technique. CPP-g-PEI had honeycomb-like pores with an average size of between 5.37 and 13.54 nm and was thermally stable up to 250 °C. CPP-g-PEI was amorphous porous polymer with some spherulites. The N content of CPP-g-PEI increased and the Cl content of CPP-g-PEI decreased after hydrothermal amination reaction. The hydrogen storage properties of different CPP-g-PEI samples were determined by a hydrogen storage analyzer. Among all samples, hydrogen storage capacity of CPP-g-PEI at 100 °C and triethylamine solvent (CPP-g-PEI-2) achieved the highest hydrogen uptake 11.26 wt% at 77 K, 5 MPa. In addition, OH⁻ type CPP-g-PEI (CPP-g-PEI_OH−) exhibited a hydrogen uptake of 2.47 wt% at 300 K, 5 MPa. BET specific surface area of the sample was not directly associated with hydrogen storage capacity. Hydrogen adsorption enthalpy of CPP-g-PEI-2 was calculated by the Arrhenius equation to be 38.79 kJ/mol and the adsorption process of CPP-g-PEI was investigated to be reversible physical adsorption.     

Low temperature milling of the LiNH2 + LiH hydrogen storage system

Ball milling of the LiNH₂ + LiH storage system was performed at 20 °C, −40 °C, and −196 °C, and the resulting powders were analyzed using X-ray diffraction, scanning electron microscopy, nuclear magnetic resonance (NMR), specific surface area analysis, and kinetics cycling measurements. Ball milling at −40 °C showed no appreciable deviations from the 20 °C sample, but the −196 °C powder exhibited a significant increase in the hydrogen desorption kinetics. NMR analysis indicates that a possible explanation for the kinetics increase is the retention of internal defects generated during the milling process that are annealed at the collision site at higher milling temperatures.     

High-pressure hydrogen storage on microporous zeolites with varying pore properties

Hydrogen storage on microporous zeolites was examined using a high pressure dose of hydrogen at 30 °C. The roles of the framework structure, surface area, and pore volume of the zeolites on hydrogen adsorption were investigated. The largest hydrogen storage was obtained on the ultra stable Y (USY) zeolite (0.4 wt%). The hydrogen adsorption isotherms on the zeolites reached a maximum after a hydrogen pressure of 50 bar. The amount of hydrogen adsorption on Mordenite (MOR) zeolites increased with increasing Si/Al molar ratio, which was achieved by dealumination. The amount of hydrogen adsorption increased linearly with increasing pore volume of the zeolites. The hydrogen adsorption behavior was found to be dependent mainly on the pore volume of the zeolites.     

Synthesis and hydrogen storage studies of metal−organic framework UiO-66

Metal−organic framework UiO-66 has high chemical and thermal stability. However, it is difficult to produce such Zr-based MOFs with good crystalline morphology. Here, highly pure metal−organic framework UiO-66 has been synthesized at low temperature (50 °C). The as-synthesized sample has been characterized by X-ray diffraction, thermogravimetric analysis, nitrogen adsorption, and scanning electron microscopy. Its hydrogen-storage capacity has been measured by means of an Intelligent Gravimetric Analyser. The results showed that UiO-66 was synthesized in octahedral crystals of well-defined sizes (150−200 nm) and had a high specific surface area (1358 m²/g). The as-synthesized UiO-66 showed a significant hydrogen uptake even at a moderate pressure, which increased to 3.35 wt% at 77 K and 1.8 MPa. A grand canonical Monte Carlo simulation (GCMC) has been employed to calculate the adsorption of hydrogen in UiO-66. The result of this simulation provided a theoretical foundation for the experimental results.     

H2 adsorption mechanism in Mg modified multi-walled carbon nanotubes for hydrogen storage

Multi-walled carbon nanotubes (MWCNTs) with diameter of about 50 nm were synthesized using thermal chemical vapor deposition. We have investigated the influence of Mg doping to the MWCNTs on its hydrogen storage property. TEM micrographs showed that Mg was attached to the MWCNTs and discontinuous arrangement of the carbon walls was recognized in the MWCNTs. According to XPS and BET analyses, the surface functional groups and pore size of the Mg-MWCNTs are increased by interactions between the Mg and the MWCNT’s outer walls. The electrochemical discharging curves of the MWCNTs and Mg-doped MWCNTs revealed that the hydrogen storage capacity was 363 and 450 mAhg⁻¹, respectively. Volumetric technique determined that the hydrogen storage capacity of the MWCNTs and Mg-MWCNTs was 0.7 and 1.5 wt%, respectively. There are likely a couple of mechanism for Mg metal that used as dopant to pure MWCNTs, one involves increasing of adsorption binding energy and desorption temperature due to increasing defect sites (oxygen functional groups), while the second explains by electron transfer from metal atoms to carbon atoms resulting in a considerable increase in both the adsorption binding energy and desorption temperature.