Accurate gas – Zeolite interaction measurements by using high pressure gravimetric volumetric adsorption method

In this work, we discuss the purification of hydrogen by physical adsorption on zeolites Li–LSX exchanged 78%, 83% and 99%. A newly developed adsorption device is applied to the gas–solid adsorption measurements. Isotherms of hydrogen adsorption are gravimetric volumetrically measured at 293.15 K up to 5 MPa. The accuracy of this new device is compared to NIST gas density data's of hydrogen and nitrogen at 293.15 K. Further the real density of the zeolites is obtained by helium skeleton density measurements at high temperature (650 K). The paper provides an interpretation of hydrogen adsorption capacities according to the gas-surface interaction. Further the isosteric heat of adsorption is obtained for the studied materials and analysed in relation to the zeolite cations exchange rate. Moreover, we discuss the influence of the ratio of cation exchange on hydrogen gas adsorption.     

Static and dynamic studies of hydrogen adsorption on nanoporous carbon gels

Although hydrogen is considered to be one of the most promising green fuels, its efficient and safe storage and use still raise several technological challenges. Physisorption in porous materials may offer an attractive means of $H_2$ storage, but the state-of-the-art capacity of these kinds of systems is still limited. To overcome the present drawbacks a deeper understanding of the adsorption and surface diffusion mechanism is required along with new types of adsorbents developed and/or optimised for this purpose. In the present study we compare the hydrogen adsorption behaviour of three carbon gels exhibiting different porosity and/or surface chemistry. In addition to standard adsorption characterisation techniques, neutron spin-echo spectroscopy (NSE) has been also applied to explore the surface mobility of the adsorbed hydrogen. Our results reveal that both the porosity and surface chemistry of the adsorbent play a significant role in the adsorption of $H_2$ in these systems.     

Cryo-adsorptive hydrogen storage on activated carbon. I: Thermodynamic analysis of adsorption vessels and comparison with liquid and compressed gas hydrogen storage

This paper presents a thermodynamic analysis of cryo-adsorption vessels for hydrogen storage. The analysis is carried out with an unsteady lumped model and gives a global assessment of the behavior of the storage system during operation (discharge), dormancy and filling. The adsorbent used is superactivated carbon AX-21™. Cryogenic hydrogen storage, either by compression or adsorption, takes advantage of the effect of temperature on the storage density. In order to store 4.1 kg H₂ in 100 L, a pressure of 750 bar at 298 K is necessary, but only 150 bar at 77 K. The pressure is further reduced to 60 bar if the container is filled with pellets of activated carbon [7]. However, adsorption vessels are submitted to intrinsic thermal effects which considerably influence their dynamic behavior and due to which thermal management is required for smooth operation. In this analysis, among energy balances for filling and discharge processes, the influence of the intrinsic thermal effects during vessel operation is presented. Hydrogen losses during normal operation as well as during long periods of inactivity are also considered. The results are compared to those obtained in low-pressure and high-pressure insulated LH₂ and CH₂ tanks.     

Hydrogen adsorption on graphene sheets and nonporous graphitized thermal carbon black at low surface coverage

Behavior of hydrogen adsorption on nonporous carbon based materials was comparatively studied for selection of an efficient carrier for catalytic metals. Graphene sheets (GS) and graphitized thermal carbon black, which respectively has a specific surface area about 220 m²/g and 36 m²/g, were selected for adsorption equilibrium testes within temperature–pressure range from 77 K–87 K and 0–1 kPa. Henry law constants were employed to calculate the second virial constants and the limit isosteric heat of adsorption. The Weeks, Chandler and Andersen (WCA) perturbing scheme and the fundamental measure theory (FMT) were used to determine the interaction energy between solid atoms and hydrogen molecules. Adsorption potential well was determined by linear interpolation based on the Boltzmann distribution approximation. It shows that the potential well between hydrogen molecules and the GS, BP280 is respectively about 33.55 K and 31.97 K, suggesting that the bonding energy between the GS and hydrogen molecules is larger than that on carbon black.     

Hydrogen adsorption on modified activated carbon

The aim of this work is to investigate hydrogen adsorption on prepared super activated carbon (AC). Litchi trunk was activated by potassium hydroxide under N₂ or CO₂ atmosphere. Nanoparticles of palladium were impregnated in the prepared-AC. Hydrogen adsorption was accurately measured by a volumetric adsorption apparatus at 77, 87, 90 and 303 K, up to 5 MPa. Experimental results revealed that specific surface area of the prepared-AC increased according to KOH/char ratio. The maximum specific surface area reached up to 3400 m²/g and total pore volume of 1.79 cm³/g. The maximum hydrogen adsorption capacity of 2.89 wt.% at 77 K and under 0.1 MPa, was obtained on these materials. The hydrogen adsorption capacity of the 10 wt.% Pd-AC was determined as 0.53 wt.% at 303 K and under 6 MPa. This amount is higher than that on the pristine AC (0.41 wt.%) under the same conditions.     

Analysis of adsorption equilibrium of hydrogen on graphene sheets

The adsorption equilibrium of hydrogen on graphene sheets (GS) was studied based on a sample of GS with S_BET = 300 m²/g at the temperatures of 77.15 K–293.15 K and the pressures of 0 MPa–6 MPa. In the meantime, the adsorptions (Excess adsorption measurements) of hydrogen on granular coconut shell SAC-02 activated carbon (S_BET = 2074 m²/g) and carbon nanofiber (CNFs, S_BET = 205 m²/g) were investigated at the pressures of 0–8 MPa and the temperature of 77.15 K. The outcomes from experiments were used to determine the parameters in Toth equation by way of Non-linear fit. The absolute adsorption amounts of hydrogen on the GS, which were calculated from the equation, were used to calculate the isosteric heat of hydrogen adsorption by use of adsorption isosteres.     

A review on adsorption cooling systems with adsorbent carbon

This study introduces a review for the potential cooling systems which uses carbon materials as an adsorbent. Also, the adsorption carbon pairs (pairs where the carbon is the adsorbent) which is still under researches were reviewed. The maximum COP (coefficient of performance) of the cooling systems was 0.8 for activated carbon/ethanol pair. The study concluded that the performances of the potential adsorption cooling systems using carbon are still not satisfied. It was concluded that there is an opportunity for the adsorption carbon pairs to introduce a new cooling system with a promising performances.     

Fabrication of Ni-MOF74 derived Ni-carbon material for the highly efficient H2 gas adsorption at mild operating condition

This study fabricates nickel nanoparticle-carbon hybrid (Ni-MOF74) composite via solvothermal technique, and carbonized at different temperature under inert atmosphere, which was then used for the hydrogen storage. Morphology, crystallinity, electronic distribution and other surface properties of the synthesized material were extensively checked via different analytical techniques. Results showed that the Ni-MOF74 sample carbonized at 500 °C displays an improved hydrogen storage capacity of～400% compared to the parent Ni-MOF74 material (0.088 vs 0.002 wt %), at 298 K and 1 atm. We believe that these Ni-carbon hybrid materials hold promising results for hydrogen storage as they show potential for storage at room temperature, and it is believed to be cost effective compared to traditionally used hydrogen spillover catalysts.     

Determination of the enthalpy of adsorption of hydrogen in activated carbon at room temperature

The development of high-performance materials for hydrogen storage by adsorption requires detailed understanding of the adsorbate-adsorbent interactions, e.g., the enthalpy of adsorption ΔH, which measures the interaction strength. The determination of ΔH for a weakly adsorbing gas such as hydrogen in a carbonaceous porous material is difficult experimentally, normally requiring measuring two cryogenic adsorption isotherms. Here we demonstrate a calculation of ΔH based on ca. room temperature adsorption isotherms at 273 K and 296 K using the Clausius-Clapeyron equation. This requires an estimation of the volume of the adsorbed film (~40%, ~12% of the total pore volume at 77 K, 296 K, respectively) obtained from fits of the excess adsorption isotherms to an Ono-Kondo model with the auxiliary use of a fixed point corresponding to the saturation film density (estimated as 100 ± 20 g/L) which appears to be remarkably sample and temperature independent, i.e., a property of the adsorbate. The calculated room temperature enthalpy of adsorption ΔH = 8.3 ± 0.4 kJ/mol is in excellent agreement with the low-coverage cryogenic determination of ΔH. The methodology hereby proposed facilitates reliable calculations of the enthalpy of adsorption at room temperatures for weakly-adsorbing gases.     

Conditioning of hydrogen storage by continuous solar adsorption in activated carbon AX-21 with simultaneous production

The capacity of hydrogen storage by solar adsorption in activated carbon AX-21 and filling rate with simultaneous production have been conditioned under a minimum pressure, to nullify the cost of energy supplied to compressor. A gas accumulator tank connected to electrolyzer and continuous adsorption beds have been proposed in the process scheme. Minimum pressure required for the tank at an ambient filling temperature fixed to 25 °C is only 2 bar. While at atmospheric filling pressure the corresponding value of filling temperature is found to be 5 °C. However, a cooling fluid at low temperature for adsorbent bed during the adsorption process will be an efficient way for increasing the stored amount of hydrogen. Almost 4.5 kg of hydrogen can be stored in an adsorbent mass of 200 kg. The adsorption flow rate has been also modelled to be controlled for being adapted to production rate.     

Tight-binding study of hydrogen adsorption on palladium decorated graphene and carbon nanotubes

In this work we report a theoretical study on the atomic and molecular hydrogen adsorption onto Pd-decorated graphene monolayer and carbon nanotubes by a semi-empirical tight-binding method. We first investigated the preferential adsorption geometry, considering different adsorption sites on the carbon surface, and then studied the evolution of the chemical bonding by evaluation of the overlap population (OP) and crystal orbital overlap population (COOP). Our results show that strong C–Pd and H–Pd bonds are formed during atomic hydrogen adsorption, with an important role in the bonding of C 2p_z and Pd 5s, 5p_z and 4d_z² orbitals. The hydrogen storage mechanism in Pd-doped carbon-based materials seems to involve the dissociation of H₂ molecule on the decoration points and the bonding between resultant atomic hydrogen and the carbon surface.     

H2 storage on single- and multi-walled carbon nanotubes

The adsorption of hydrogen on single-walled and multi-walled carbon nanotubes (CNTs) was investigated at 77 and 298 K, in the pressure range of 0–1000 Torr. The adsorption isotherms indicate that adsorption follows the Langmuir model. Hydrogen uptakes were found to depend strongly on the nature of the CNTs. Single-walled CNTs adsorb significantly higher quantities of hydrogen per unit mass of the solid, while the opposite is true on a per unit surface area basis. This observation implies that adsorption takes place selectively on specific sites on the surface. The hydrogen uptake capacity of CNTs was also found to be affected by the purity of the materials, increasing with increasing purity. Temperature programmed desorption indicated that relatively strong adsorption bonds develop between adsorbent and adsorbate and that a single type of adsorption site exists on the solid surface.     

Hydrogen storage properties of carbon aerogel synthesized by ambient pressure drying using new catalyst triethylamine

In this paper, we report here the hydrogen storage capacity of activated carbon aerogel synthesized by ambient pressure drying using a new catalyst. The carbon aerogel (CA) has been synthesized by the sol-gel method using resorcinol (R) and formaldehyde (F). For drying of RF wet gel instead of expensive and unsafe supercritical process, we have used ambient pressure drying. To avoid shrinkage which may occur due to this mode of drying, instead of usual catalyst (C): Na₂CO₃, organic catalyst triethylamine (TEA), which is known to be a condensing agent has been used. In order to find out the effect of change of R/C ratio on hydrogen sorption, three different R/C namely CA 1000, CA 2000, and CA 3000 were taken. Structural and microstructural details have been studied employing XRD, SEM, TEM, nitrogen adsorption, FTIR, and Raman spectroscopy. TEM and nitrogen adsorption studies have revealed that aerogel with R/C 1000 exhibits a higher degree of micropore density. The hydrogen storage capacities for all R/C ratios have been determined. It has been found that carbon aerogel (CA) with R/C = 1000, exhibits the highest hydrogen adsorption capacity out of the three aerogels. At liquid nitrogen temperature, the hydrogen storage capacity of aerogel with R/C = 1000 for the as-synthesized and activated carbons have been found to be 4.00 wt % and 4.80 wt %. A viable reason for the occurrence of high hydrogen storage capacity at liquid nitrogen temperature for aerogel with R/C = 1000 has been put forward.     

Data-driven modelling and optimization of hydrogen adsorption on carbon nanostructures

In the present study, using modelling based on experimental data, models for predicting the hydrogen adsorption isotherm were presented. The three Automatic Learning of Algebraic Models (ALAMO), feed-forward artificial neural networks (ANNs), and group method of data handling-type polynomial neural networks (GMDH-PNN) were constructed. The created models were evaluated to predict the equilibrium data of hydrogen storage on carbon nanostructures, including activated carbons doped with palladium (Pd) nanoparticles, fullerene pillared graphene nanocomposites, and nickel (Ni)-decorated carbon nanotubes. The inputs were nanostructure characteristics such as surface area, pore-volume, and thermodynamic conditions such as pressure. The generalization of the trained models was acceptable, and the models successfully predicted the hydrogen adsorption isotherm for new inputs. The relative error percentage for most data points is less than 4%, which demonstrates their applicability in determining adsorption isotherms for any operating conditions. By performing error analysis calculations, it was shown that the ALAMO model has the highest accuracy. Also, sensitivity analysis calculations show that pressure is the most influential parameter in the adsorption process. Besides, by performing Genetic Algorithm (GA) optimization using the ALAMO model, the amount of pressure and adsorbent properties were determined so that the amount of hydrogen adsorption is maximized. According to the optimization results based on the GA, the higher the pressure, the greater the amount of hydrogen adsorption. The nanotubes with a surface area of 194.15 m²/g, a total volume of 1.8 cm³/g, micropore volume of 0.097 cm³/g, and mesopore volume of 0.963 cm³/g, graphene with a surface area of 2977.13 m²/g, a total volume of 1.5134 cm³/g, density of 617.45 kg/m³, and activated carbon at pressures less than 30 bar with a surface of 2546.36 m²/g, a total volume of 1.237 cm³/g, micropore volume of 0.839 cm³/g, and activated carbon at pressures more than 30 bar with a surface of 3027 m²/g, a total volume of 1.343 cm³/g, a micropore volume of 0.9582 cm³/g, and a mesopore volume of 1.23 cm³/g, have the highest amount of stored hydrogen.     

H2 adsorption in Ni and passivated Ni doped 4 Å single walled carbon nanotube

Adsorption binding energies have been calculated for Nickel-doped single-walled carbon nanotubes (CNTs). Density Functional Theory (DFT) with double numerical polarization (DNP) has been used for finding the total energies of the structures. It is found that the Nickel doped CNTs show fluctuation in the binding energies of hydrogen adsorption which is overcome by passivating the Nickel atom with two hydrogen atoms. The density of states (DOS) and Mullikan atomic charge analysis have been carried to confirm the charge transfer from Ni to the carbon atoms of the CNT. The smallest CNT (diameter ≈ 4 Å) with the chirality of (5,0) has been taken for hydrogen adsorption studies. Geometry optimization shows that Ni atom prefers bridge site rather than the centre of the hexagon. The H₂ binding energies obtained in the present study reveal that desorption would take place above room temperature in Ni doped (5,0) CNTs.     

Synergetic effect of carbon self-doping and TiO2 deposition on boosting the visible-light photocatalytic hydrogen production efficiency of carbon nitride

To improve the visible light utilization and photogenerated carriers separation, carbon self-doped carbon nitride (C-CN) supported TiO₂ photocatalysts were synthesized via a designed two-step strategy. After carbon self-doping, the colloid TiO₂ were in-situ deposited on C-CN surface and crystalized by calcination. Simultaneously, the bulk C-CN structure was thermally exfoliated to nanosheet morphology. This strategy ensured the saturated deposition of colloid TiO₂ nanoparticles on C-CN nanosheets to form well-constructed heterostructure with sufficient interfacial contact. The as-prepared TiO₂/C-CN (TCN) heterojunction photocatalysts showed enhanced visible light absorption capability, resulting in impressively high hydrogen production efficiency as 212.7 μmol h⁻¹, which was 10.8 times higher than that of CN. The remarkably enhanced photocatalytic performance may be mainly ascribed to synergetic effect of carbon self-doping and TiO₂ deposition on the improved visible light utilization and photogenerated carriers separation. The probable mechanism in such well-constructed heterojunction photocatalysts was proposed based on the structural analysis, electrical and photoelectrical properties, and photocatalytic process. The proposed strategy may be extended to the preparation of diverse heterojunction photocatalysts with excellent performance for solar energy conversion.     

Cryo-adsorptive hydrogen storage on activated carbon. II: Investigation of the thermal effects during filling at cryogenic temperatures

This paper presents an investigation of the thermal effects during high pressure filling of a cryo-adsorptive hydrogen storage tank. The adsorbent is powdered activated carbon. A two-dimensional model is formulated, which describes hydrodynamics, heat transfer and adsorption phenomena in cylindrical tanks. Experiments with a tank containing about 10 kg of adsorbent were carried out to parameterize and validate the model. Good agreement between experiments and simulations could be obtained. Numerical results are then presented concerning filling processes. Two cooling concepts are investigated: a LN₂ cooling jacket and a recirculation system which uses the hydrogen itself as the cooling fluid. The results show that short filling times can only be achieved with the recirculation system.     

Implications of non-uniform porosity distribution in gas diffusion layer on the performance of a high temperature PEM fuel cell

The present study discusses a detailed investigation on the implications of non-uniform porosity distribution in the gas diffusion layer (GDL) on the performance of proton exchange membrane fuel cell (PEMFC). A three-dimensional, single-phase, isothermal model of high-temperature PEMFC is employed to study the effect of non-uniform porosity distribution in GDL. The different porosity configurations with stepwise, sinusoidal, and logarithmic variation in porosity along the streamwise direction of GDL are considered. The numerical experiments are performed, keeping average porosity as constant in the GDL. The electrochemical characteristics such as the oxygen molar concentration, power density, current density, total power dissipation density, average diffusion coefficient, vorticity magnitude, and overpotential are studied for a range of porosity distributions. Furthermore, the variations of oxygen concentration, average diffusion coefficient, and vorticity magnitude are also discussed to showcase the influence of non-uniform porosity distribution. Our study reveals that the PEM fuel cell performance is the best when the porosity of the GDL decreases logarithmically in the streamwise direction. On the contrary, the performance deteriorates when the GDL porosity decreases sinusoidally. Also, it has been observed that the effects of non-uniform porosity distribution are more pronounced, especially at higher current densities. The outcomes of present investigation have potential utility in GDL fabrication and membrane assembly's sintering process for manufacturing high valued PEMFC products.     

Effect of different reductants for palladium loading on hydrogen storage capacity of double-walled carbon nanotubes

The effects of different reductants for palladium loading on the hydrogen sorption characteristics of double-walled carbon nanotubes (DWCNTs) have been investigated. Pd nanoparticles were loaded on DWCNT surfaces for dissociation of H₂ into atomic hydrogen, which spills over to the defect sites on the DWCNTs. When we use different reductants, the reduction capabilities and other effects of the different reductants are different, which affects the hydrogen storage capacity of the DWCNTs. In this work, the amount of hydrogen storage capacity was determined (by AMC Gas Reactor Controller) to be 1.7, 2.0, 2.55, and 3.0 wt% for pristine DWCNTS and for 2.0%Pd/DWCNTs using H₂, l-ascorbic acid, and NaBH₄ as reductants, respectively. We found that the hydrogen storage capacity can be enhanced by loading with 2% Pd nanoparticles and selecting a suitable reductant. Furthermore, the sorption can be attributed to the chemical reaction between atomic hydrogen and the dangling bonds of the DWCNTs.     

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.