Hydrogen storage on chemically activated carbons and carbon nanomaterials at high pressures

Hydrogen adsorption measurements have been carried out at different temperatures (298 K and 77 K) and high pressure on a series of chemically activated carbons with a wide range of porosities and also on other types of carbon materials, such as activated carbon fibers, carbon nanotubes and carbon nanofibers. This paper provides a useful interpretation of hydrogen adsorption data according to the porosity of the materials and to the adsorption conditions, using the fundamentals of adsorption. At 298 K, the hydrogen adsorption capacity depends on both the micropore volume and the micropore size distribution. Values of hydrogen adsorption capacities at 298 K of 1.2 wt.% and 2.7 wt.% have been obtained at 20 MPa and 50 MPa, respectively, for a chemically activated carbon. At 77 K, hydrogen adsorption depends on the surface area and the total micropore volume of the activated carbon. Hydrogen adsorption capacity of 5.6 wt.% at 4 MPa and 77 K have been reached by a chemically activated carbon. The total hydrogen storage on the best activated carbon at 298 K is 16.7 g H₂/l and 37.2 g H₂/l at 20 MPa and 50 MPa, respectively (which correspond to 3.2 wt.% and 6.8 wt.%, excluding the tank weight) and 38.8 g H₂/l at 77 K and 4 MPa (8 wt.% excluding the tank weight).     

Hydrogen adsorption studies on single wall carbon nanotubes

Hydrogen adsorption data on as-grown and heat-treated single walled carbon nanotubes (SWNTs) obtained by a volumetric procedure using a Quantachrome Autosorb-1 equipment are presented. The amounts of hydrogen adsorbed at atmospheric pressure reach approximately 0.01 wt.% at 298 K and 1 wt.% at 77 K. The isosteric heat of adsorption has been calculated for both samples from H₂ equilibrium adsorption data at three temperatures, having initial values of 7.42 and 7.75 kJ mol⁻¹. Studies in porous structure by N₂ adsorption and density measurements in helium pycnometer are reported.     

Hydrogen adsorption on partially truncated and open cage C60 fullerene

C₆₀ buckyball molecules were partially truncated by a controlled oxidation at 400 °C and 2 bar oxygen pressure to create unique pore textures suitable for hydrogen adsorption. Pore textural analysis and density measurement confirmed the success of cage-opening and the creation of pore structures accessible to gas molecules. The specific surface area of the C₆₀ sample were increased from below detection to a measurable value (BET: 85 m²/g). Raman spectral study showed that the three main bands of C₆₀, H_g(1), A_g(1) and A_g(2) remained and significant defects were created after the C₆₀ fullerenes were partially oxidized. XRD and SEM measurements suggested that the C₆₀ fullerenes lost their crystallinity and the crystal surfaces were etched after the oxidation step. Hydrogen adsorption on the C₆₀ fullerenes were measured at three temperatures (77, 143 and 228 K) and hydrogen pressures up to 150 bar. Hydrogen adsorption capacity on C₆₀ fullerenes at 77 K at 120 bar was more than tripled (from 3.9 to 13 wt.%) after the C₆₀ fullerenes were partially oxidized. The average heat of adsorption of hydrogen on the partially oxidized C₆₀ fullerene molecules (2.38 kJ/mol) is within the range of the reported values of heat of adsorption on other porous adsorbents.     

High hydrogen uptake capacity of mesoporous nitrogen-doped carbons activated using potassium hydroxide

Mesoporous nitrogen-doped carbons activated using potassium hydroxide have large surface areas and high pore volumes, are studied for their hydrogen storage properties. The activated material can store 6.84 wt.% of hydrogen at 77 K under a pressure of 20 bar, which is estimated to correspond to a maximum capacity of 8.24 wt.% based on the Langmuir simulation. The hydrogen adsorption values show linear relationships with the volumes of micropores and small mesopores under those conditions, which indicates that the small mesopores between the sizes 2 and 3 nm also make contributions to the hydrogen adsorption at high pressure.     

Characterization of Cabot non-graphitized carbon blacks with a defective surface model: Adsorption of argon and nitrogen

A grand canonical Monte Carlo simulation (GCMC) is used to study the adsorption of argon and nitrogen on non-graphitized carbon black. The surface is assumed to be finite in length and composed of three graphene layers, the top layer of which contains defects. The isotherm obtained for the non-graphitized carbon shows a smooth S-shaped type while that obtained for the perfect graphene layer shows a wavy type. The isosteric heat is also affected by the defect; its behaviour versus loading exhibits a decrease at the beginning and then slightly increases once the first layer has been formed. The decreasing behaviour of isosteric heat at low loadings is not observed in the case of graphitized carbon black. The simulated results are compared against the experimental data of argon and nitrogen at 77 and 87.3 K on the Cabot carbon black BP 280, 460 and 2000. It is found that the defected finite surface describes well the data of these blacks. For the case of BP 2000 we have found that besides the defects of the surface, this sample contains a small population of small micropores having a width of 8.2 Å and its specific pore volume of 0.08 cm³/g.     

The dependence of the hydrogen sorption capacity of single-walled carbon nanotubes on the concentration of catalyst

The adsorption of hydrogen on single-walled carbon nanotubes was measured using micro-gravimetric nitrogen and hydrogen adsorption isotherms at 77 K for gas pressures of up to 1 bar (nitrogen) and 12 bar (hydrogen). Results show that surface area and hydrogen uptake depend on the concentration of the iron catalyst used for making the nanotubes. Langmuir fits to the hydrogen uptake curves clearly show two adsorption energies for each sample which we attribute to the groove site for the higher adsorption energy and to the convex tube surface for the lower energy. We also present calculations of the binding energy of hydrogen on these same sites on SWCNTs and confirm that the groove site has a significantly higher (radius-dependent) binding energy than the surface site, consistent with the experimental values. This suggests that the use of the Langmuir model is appropriate to the adsorption of H2 on activated carbons for the temperature and pressure range investigated and could be used as a rapid way of estimating the average tube radius in the sample.     

Experimental evidence of an upper limit for hydrogen storage at 77 K on activated carbons

An upper limit for hydrogen storage at 77 K on activated carbons was clearly observed in the present experimental work. Such a limit is around 6.4 wt.%, i.e., close to the theoretical limit of 6.8 wt.%. Results of hydrogen storage were obtained in three independent laboratories using volumetric and gravimetric devices. Lab-made activated carbons (ACs) were found to have higher capacities than those of the commercial material AX-21. A maximum excess hydrogen storage capacity of 6.0 wt.% at 77 K and 4 MPa was obtained. This maximum was reduced to 0.6 wt.% at 298 K and 5 MPa. ACs with surface areas (S_BET) as high as 3220 m² g⁻¹ were prepared from chemical activation of anthracites with alkali (Na and K) hydroxides. At 77 K and 4 MPa, excess hydrogen storage capacity was directly correlated with S_BET for ACs having S_BET values lower than 2630 m²/g. Hydrogen uptake at 77 K also correlated with micropore volume and strongly depended on average pore diameter.     

Numerical estimation of hydrogen storage limits in carbon-based nanospaces

Theoretical limits of the hydrogen adsorption in carbon nanospaces are modeled using Monte Carlo simulations. A detailed analysis of storage capacity of slit pores has been performed as a function of the pore size, gas pressure (up to 100 bars) and temperature of adsorption (77 and 298 K). The H₂-slit wall interaction has been modeled assuming energies of adsorption ranging from 4.5 kJ/mol (pure graphene surface) to 15 kJ/mol (hypothetical chemically modified graphene). The quantum nature of H₂ has been incorporated in the calculations using the Feynman-Hibbs approach. It has been shown that in a hypothetical chemically modified porous carbon, with energy of adsorption of 15 kJ/mol or higher and pore size between 0.8 and 1.1 nm, the gravimetric and volumetric storage capacity can achieve targets required for practical applications. The relation between the energy of adsorption and the effective delivery has been discussed.     

Synthesis, characterization and energy-related applications of carbide-derived carbons obtained by the chlorination of boron carbide

A nanoporous carbide-derived carbon (CDC) was synthesized by chlorination of boron carbide powder using hydrogen chloride as the reactive gas. The structure and texture of the CDCs were characterized by X-ray diffraction, high-resolution transmission electron microcopy and nitrogen adsorption at 77 K, which confirmed a structural and textural dependence on chlorination temperature and reaction time. The CDC technique to produce porous carbons is very attractive because it can obtain carbons with desired structure and porosity and the CDCs produced here show great potential for energy-related applications. Used as hydrogen storage materials, the hydrogen uptake capacity could reach 1.06 wt.% at 77K and 1 bar. When tested as electrodes for supercapacitors, specific surface capacitance value up to 0.403 F m⁻² and a capacitance retention ratio up to 86% (at a voltage scan rate of 50 mV s⁻¹) could be obtained.     

Enhanced hydrogen storage capacity in carbon aerogels treated with KOH

Organic aerogels are prepared by the sol-gel polymerization of resorcinol with furfural catalysed by potassium hydroxide solution using ambient pressure drying. These aerogels are further carbonised in nitrogen in order to obtain their corresponding carbon aerogels. Nitrogen adsorption at 77 K allowed the determination of surface areas and pore volumes, further analysed by the Dubinin-Radushkevich model and density functional theory model. In particular, a KOH catalysed carbon aerogel exhibits a hydrogen uptake of ∼5.2 wt.% at 77 K and 3.5 MPa. The correlation of maximum hydrogen uptake with surface area and micropore volume was investigated.     

The rotational and translational dynamics of molecular hydrogen physisorbed in activated carbon: A direct probe of microporosity and hydrogen storage performance

We have measured Incoherent Inelastic Neutron Scattering (IINS) spectra of H₂ physisorbed in high purity chemically activated carbon (AC) at different surface coverage and at temperatures near the triple point of bulk hydrogen. Our experimental results and DFT calculations show that at low surface coverage, due to the very low corrugation of the adsorption potential, and in the absence of H₂-H₂ lateral interactions, the adsorbed molecules are practically free to translate in the 2D plane parallel to the surface. Model calculations show that a complete mixing between the sub-states of the J = 1 manifold occurs on the free surface. The J = 0-to-1 rotational transition should split if the H₂ molecule is adsorbed in a slit type pore. Rotational splitting of up to 13 meV is found in the narrowest pores of around 6 Å investigated. The calculated isosteric heat of adsorption for molecules adsorbed on the free surface, at different sites and molecule orientations, range between −39 and −42 meV/H₂ at 77 K. In the optimum size slit pores, these numbers double up. Micropore volume of 0.34-0.45 ml/g carbon, and an upper limit of 4 wt% hydrogen storage is anticipated for the investigated material.     

High surface area carbide-derived carbon fibers produced by electrospinning of polycarbosilane precursors

Highly porous carbide-derived carbon fibers have been synthesized by electrospinning of polycarbosilane with subsequent pyrolysis and chlorination. The resulting ultrathin fibers show specific surface areas up to 3116 m² g⁻¹ and very high storage capacities for hydrogen up to 3.86 wt.% at 17 bar and 77 K. Due to the outstanding adsorption performance and other properties such as high temperature stability and the unique CDC fiber shape, this new kind of fiber material offers promising possibilities for several applications like air or liquid filters or textiles for protective clothing. Application as a flexible electrode material for supercapacitors is conceivable.     

Activation, characterization and hydrogen storage properties of the mesoporous carbon CMK-3

Activation of mesoporous carbon CMK-3 with CO₂ for hydrogen storage was studied. Huge structure and texture changes emerged for the activated CMK-3 based on the characterization by using XRD, TEM and nitrogen adsorption at 77 K. The ordered mesoporous structure of CMK-3 gradually became disorder and its specific surface area and volume of pores especially micropores were enhanced remarkably. Hydrogen sorption measurement showed that the activation led to an obvious increase of the H₂ sorption capacity of CMK-3. The maximum H₂ uptake of 2.27 wt% at 77 K and 1 bar was obtained for the sample activated at 1223 K for 8 h. The small pores with the diameter smaller than 1 nm contributed greatly to the H₂ uptake, and were confirmed more effective than other pores for hydrogen storage.     

Structure and hydrogen adsorption properties of low density nanoporous carbons from simulations

We systematically model the hydrogen adsorption in nanoporous carbons over a wide range of carbon bulk densities (0.6–2.4 g/cm³) by using tight binding molecular dynamics simulations for the carbon structures and thermodynamics calculations of the hydrogen adsorption. The resulting structures are in good agreement with the experimental data of ultra-microporous carbon (UMC), a wood-based activated carbon, as indicated by comparisons of the microstructure at atomic level, pair distribution function, and pore size distribution. The hydrogen adsorption calculations in carbon structures demonstrate both a promising hydrogen storage capacity (excess uptake of 1.33 wt.% at 298 K and 5 MPa, for carbon structures at the lower range of densities) and a reasonable heat of adsorption (12–22 kJ/mol). This work demonstrates that increasing the heat of adsorption does not necessarily increase the hydrogen uptake. In fact, the available adsorption volume is as important as the isosteric heat of adsorption for hydrogen storage in nanoporous carbons.     

Carbon aerogels from acetic acid catalysed resorcinol-furfural using supercritical drying for hydrogen storage

Organic aerogels were derived from acetic acid catalysed resorcinol and furfural and then dried directly in supercritical carbon dioxide without the use of a solvent exchange process. These aerogels were further carbonised in nitrogen and activated in CO₂ in order to obtain their corresponding carbon aerogels. The carbon aerogels prepared by this method had a greater proportion of micropores in addition to a much shorter preparation time (on the order of days) than those prepared by other studies. The effect of different drying techniques on the microstructure of the wet gels was investigated by nitrogen adsorption at cryogenic liquid nitrogen temperature. Nitrogen adsorption at 77 K allowed the determination of surface areas and pore volumes, further analysed by the Dubinin-Radushkevich model and density functional theory model. The surface area and micropore volume of carbon aerogels prepared by this method increased by 19% and 12%, and accordingly, hydrogen uptake capacity was increased by 10% from 4.9 ± 0.2 wt.% to 5.4 ± 0.3 wt.% at 4.6 MPa and 77 K.     

Hydrogen adsorption in different carbon nanostructures

Hydrogen adsorption in different carbonaceous materials with optimized structure was investigated at room temperature and 77 K. Activated carbon, amorphous carbon nanotubes, SWCNTs and porous carbon samples all show the same adsorption properties. The fast kinetics and complete reversibility of the process indicate that the interaction between hydrogen molecules and the carbon nanostructure is due to physisorption. At 77 K the adsorption isotherm of all samples can be explained with the Langmuir model, while at room temperature the storage capacity is a linear function of the pressure. The surface area and pore size of the carbon materials were characterized by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. A linear relation between hydrogen uptake and specific surface area (SSA) is obtained for all samples independent of the nature of the carbon material. The best material with a SSA of 2560 m²/g shows a storage capacity of 4.5 wt% at 77 K.     

Preparation of functionalized graphene sheets by a low-temperature thermal exfoliation approach and their electrochemical supercapacitive behaviors

Two kinds of functionalized graphene sheets were produced by thermal exfoliation of graphite oxide. The first kind of functionalized graphene sheets was obtained by thermal exfoliation of graphite oxide at low temperature in air. The second kind was prepared by carbonization of the first kind of functionalized graphene sheets at higher temperature in N₂. Scanning electron microscopy images show that both two kinds of samples possess nanoporous structures. The results of N₂ adsorption-desorption analysis indicate that both of two kinds of samples have high BET surface areas. Moreover, the second kind of functionalized graphene sheets has a relatively higher BET surface area. The results of electrochemical tests is as follows: the specific capacitance values of the first kind of functionalized graphene sheets in aqueous KOH electrolyte are about 230 F g⁻¹; the specific capacitance values of the second kind of functionalized graphene sheets with higher BET surface areas are only about 100 F g⁻¹; however, compared with the first kind of functionalized graphene sheets, the second kind has a higher capacitance retention at large current density because of its good conductive behaviors; furthermore, in non-aqueous EC/DEC electrolyte, the specific capacitance values of the first kind sample and the second kind sample are about 73 F g⁻¹ and 36 F g⁻¹, respectively.     

Experimental measurements and computer simulation of methane adsorption on activated carbon fibers

Three activated carbon fibers (ACFs) with different BET specific surface areas (SSAs) were prepared. Experimental characterization and methane adsorption on the ACFs were measured by the intelligent gravimetric analyzer (IGA-003, Hiden) at 258 and 298 K. Correlations proposed between the methane adsorption capacity and SSA indicate that the SSA plays an important role on storage amount at a given temperature. A detailed experimental investigation was focused on the sample ACF3 of the highest SSF of 1511 m²/g at five temperatures, from 258 to 298 K. The temperature dependence for methane adsorption amount on ACF3 at 1.8 MPa is proposed. It shows that temperature is vital to methane storage capacity for ACF3, and adsorption storage at the temperatures below 280 K is recommended for favorite uptakes. To model ACF3, the pores are described as slit-shaped with a pore size distribution that was determined by molecular simulation and the statistics integral equation. Predictions of methane adsorption, carried out at 258 and 298 K and high pressures by molecular simulation, indicate that our sample ACF3 can reach the uptake of 14.99 wt% at 4.0 MPa and 298 K, which is comparable with the best result in the literature.     

Influence of sample cell physisorption on measurements of hydrogen storage of carbon materials using a Sieverts apparatus

In recent years, large fluctuations have been reported for measurements of the hydrogen storage of carbon materials using a Sieverts apparatus. To investigate this problem, helium gas adsorption was selected for comparison with the adsorption of hydrogen, and the results show that hydrogen but not helium was adsorbed onto the wall of the sample cell at ambient temperature. The adsorption capacity of the sample cell at 77 K is higher than that at ambient temperature. A series of adsorption tests was conducted with a LaNi₅ alloy to prove the influence of the physisorption, and the results show that an increase in the hydrogen storage capacity was resulted in when sample loading decreases. After correction for this hydrogen physisorption, the capacity was restricted between 1.38 and 1.41 wt.%. Multi-walled carbon nanotubes (MWCNTs), activated carbon (AC), single-walled carbon nanotubes (SWCNTs), graphite nanofibers (GNFs), and graphite oxide (GO) were also measured and corrected through this method.     

The optimum average nanopore size for hydrogen storage in carbon nanoporous materials

A thermodynamical model of hydrogen storage in slitpores is presented and applied to carbon and BN nanoporous materials. The model accounts for the quantum effects of the molecules in the confining potential of the slitpores. A feature of the model is a new equation of state (EOS) of hydrogen, valid over a range of pressures wider than any other known EOS, obtained using experimental data in the range 77-300 K and 0-1000 MPa, including data in the region of solid hydrogen. The model reproduces the experimental hydrogen storage properties of different samples of activated carbons and carbide-derived carbons at 77 and 298 K and at pressures between 0 and 20 MPa, for an average nanopore width of about 5 Å. The model predicts that in order to reach the US Department of Energy hydrogen storage targets for 2010, the nanopore widths should be equal to or larger than 5.6 Å for applications at low temperatures, 77 K, and any pressure, and about 6 Å for applications at 300 K and at least 10 MPa.