Comparison of theoretical methods of the hydrogen storage capacities of nanoporous carbons

The hydrogen storage capacities of nanoporous carbons, simulated as graphene slit-shaped pores, have been calculated using simple theoretical methods that do not involve computationally expensive calculations. The theoretical methods calculate the storage of hydrogen molecules on a solid porous material by using the Equation Of State, EOS, of the hydrogen gas and the interaction potential energy of H₂ with the surfaces of the pores of the material. Calculations have been carried out using the same interaction potential energy and empirical EOS. The interaction potential energy is obtained from calculations of H₂ on graphene, using a DFT-based method that includes the dispersion interactions. The storage capacities have been calculated as a function of pressure in the range 0.1–25 MPa, of pore width in the range 4.7–20 Å and at 80.15 and 298.15 K. The storage capacities obtained with the methods are compared and the advantages and limitations of the methods are discussed, as well as the storage capacities predicted by the methods for wide pores. These simple theoretical methods are useful to design novel materials for hydrogen storage.     

Simulation of the hydrogen storage in nanoporous carbons with different pore shapes

We have used a quantum-thermodynamical model to calculate the hydrogen storage capacities of nanoporous carbons at different temperatures and pressures as a function of the shape (planar, cylindrical and spherical) and size of the pores. Three different hydrogen-carbon surface interaction potentials, based on Lennard-Jones (LJ), Møller-Plesset (MP2), and Density Functional Theory (DFT) calculations, respectively, have been used with that model, in order to obtain sensible boundaries of the values of the storage capacities. We support the MP2 results as the most realistic of the three. The optimal pore sizes, which yield the highest storage capacities, depend mainly on the shape of the pore and on the interaction potential, and slightly on temperature and pressure. At 300 K and 10 MPa, the optimal width of the planar pores and the optimal radii of the cylindrical and spherical pores lie in the ranges of 5.8-7.5, 7.0-8.6 and 8.5-10.7 Å, respectively, for the three interaction potentials considered. These values are consistent with experiments for activated carbons and activated carbon fibers. The predictions of our simulations may be useful to design nanoporous carbons with optimal hydrogen storage capacities.     

Enhanced hydrogen sorption in single walled carbon nanotube incorporated MIL-101 composite metal-organic framework

Metal-Organic Frameworks (MOFs) have emerged as potential hydrogen storage media due to their high surface area, pore volume and adjustable pore sizes. The large void space generated by cages in MOFs is not completely utilized for hydrogen storage application owing to weak interactions between the walls of MOFs and H₂ molecules. These unutilized volumes in MOFs can be effectively utilized by incorporation of other microporous materials such as single walled carbon nanotubes into the pores of MOFs which could effectively tune the pore size and pore volume of the material towards hydrogen sorption. Single walled carbon nanotubes (SWNT) incorporated MIL-101 composite MOF material (SWNT@MIL-101) was synthesized by adding purified single walled carbon nanotube (SWNT) in situ during the synthesis of MIL-101. The powder X-ray diffraction patterns of SWNT@MIL-101 showed the structure of MOF was not disturbed by SWNT incorporation. Hydrogen sorption capacities of MIL-101 was observed to increase from 6.37 to 9.18 wt% at 77 K up to 60 bar and from 0.23 to 0.64 wt% at 298 K up to 60 bar. The increment in the hydrogen uptake capacities of composite MOF materials was attributed to the decrease in the pore size and enhancement of micropore volume of MIL-101 by single walled carbon nanotube incorporation.     

First-principles study on hydrogen storage by graphitic carbon nitride nanotubes

First-principles calculations based on density functional theory were carried out to investigate the hydrogen storage capacity of graphitic carbon nitride nanotubes. Graphitic carbon nitride nanotubes could be attractive hydrogen sorbent for two reasons: firstly, its porous structure allows easy access of hydrogen into the interior of the nanotubes; and secondly, the doubly bonded nitrogen at its pore edges provides active sites for either the adsorption of hydrogen (chemically and physically), or functionalization with metal catalysts. Our calculations show that an isolated nanotube can uptake up to 4.66 wt. % hydrogen, with an average overall hydrogen adsorption energy of about −0.22 eV per H atom. In the form of a bulk bundle, the hydrogen storage capacity is enhanced due to the increased availability of space among the tubes. We predict that the hydrogen storage capacity in the bundle is at least 5.45 wt. %. Importantly, hydrogen molecules can easily access the tube’s interior due to the low energy barrier (∼0.54 eV) for their passage through the pores, indicating a fast uptake rate at relatively low pressure and temperature. Our findings show that graphitic carbon nitride nanotubes should be applicable to practical hydrogen storage because of the high gravimetric capacity and fast uptake rate.     

Room-temperature hydrogen storage performance of metal-organic framework/graphene oxide composites by molecular simulations

Metal-organic framework/graphene oxide (MOF/GO) composites have been regarded as potential room-temperature hydrogen storage materials recently. In this work, the influence of MOF structural properties, GO functional group contents and different amounts of doped lithium (Li⁺) on hydrogen storage performance of different MOF/GO composites were investigated by grand canonical Monte Carlo (GCMC) simulations. It is found that MOF/GO composites based on small-pore MOFs exhibit enhanced hydrogen storage capacity, whereas MOF/GO based on large-pore MOFs show decreased hydrogen storage capacity, which can be ascribed to the novel pores at MOF/GO interface that favors the enhanced hydrogen storage performance due to the increased pore volume/surface area. By integrating the small-pore MOF-1 with GO, the hydrogen storage capacity was enhanced from 9.88 mg/go up to 11.48 mg/g. However, the interfacial pores are smaller compared with those in large-pore MOFs, resulting in significantly reduced pore volume/surface area as well as hydrogen storage capacities of large-pore MOF/GO composite. Moreover, with the increased contents of hydroxyl, epoxy groups as well as carboxyl group modification, the pore volumes and specific surface areas of MOF/GO are decreased, resulting in reduced hydrogen storage performance. Furthermore, the room-temperature hydrogen storage capacities of Li⁺ doped MOF/GO was improved with increased Li⁺ at low loading and decrease with the increased Li⁺ amounts at high loading. This is due to that the introduced Li⁺ effectively increases the accessible hydrogen adsorption sites at low Li⁺ loading, which eventually favors the hydrogen adsorption capacity. However, high Li⁺ loading causes ion aggregation that reduces the accessible hydrogen adsorption sites, leading to decreased hydrogen storage capacities. MOF-5/GO composites with moderate Li⁺ doping achieved the optimum hydrogen storage capacities of approximately 29 mg/g.     

Hydrogen storage on silicon,carbon, and silicon carbide nanotubes: A combined quantum mechanics and grand canonical Monte Carlo simulation study

Grand canonical Monte Carlo (GCMC) simulation combined with ab initio quantum mechanics calculations were employed to study hydrogen storage in homogeneous armchair open-ended single walled silicon nanotubes (SWSiNTs), single walled carbon nanotubes (SWCNTs), and single walled silicon carbide nanotubes (SWSiCNTs) in triangular arrays. Two different groups of nanotubes were studied: the first were (12,12) SiNTs, (19,19) CNTs, and (15,15) SiCNTs and the second were (7,7) SiNTs, (11,11) CNTs, and (9,9) SiCNTs with the diameters of ∼26 and ∼15 Å for the first and second groups, respectively. The simulations were carried out for different thermodynamic states. The potential energy functions (PEFs) were calculated using ab initio quantum mechanics and then fitted with (12,6) Lennard-Jones (LJ) potential model as a bridge between first principles calculations and GCMC simulations. The absolute, excess, and delivery adsorption isotherms of hydrogen were calculated for two groups of nanotubes. The isosteric heat of adsorption and the radial distribution functions (RDFs) for the adsorbed molecules on different nanotubes were also computed. Different isotherms were fitted with the simulation adsorption data and the model parameters were correlated. According to the results, the hydrogen uptake values in (19,19) CNT array exceeded the US DOE (Department of Energy) target of 6.0 wt% (FY 2010) at 77 K and 1.0 and 2.0 MPa for absolute and excess uptakes, respectively. The results also show that SiNTs and SiCNTs are not more useful materials compared with corresponding CNTs for hydrogen storage.     

Simulations of volumetric hydrogen storage capacities of nanoporous carbons: Effect of dispersion interactions as a function of pressure,temperature and pore width

Simulations of the hydrogen storage capacities of activated carbons require an accurate treatment of the interaction of a hydrogen molecule physisorbed on the graphitic-like surfaces of nanoporous carbons, which is dominated by the dispersion interactions. These interactions are described accurately by high level quantum chemistry methods such as the Coupled cluster method with single and double excitations and a non-iterative correction for triple excitations (CCSD(T)), but those methods are computationally very expensive for large systems and massive simulations. Density functional theory (DFT) based methods that include dispersion interactions are less accurate, but computationally less expensive. Calculations of the volumetric hydrogen storage capacities of nanoporous carbons, simulated as benzene and graphene slit-shaped pores, have been carried out, using a quantum-thermodynamic model of the physisorption of H₂ on surfaces and the interaction potential energy curves of H₂ physisorbed on benzene and graphene obtained using the CCSD(T) and second order Møller-Plesset (MP2) methods and the 14 most popular DFT-based methods that include the dispersion interactions at different levels of complexity. The effect of the dispersion interactions on the DFT-based volumetric capacities as a function of the pressure, temperature and pore width is evaluated. The error of the volumetric capacities obtained with the quantum-thermodynamic model and each method is also calculated and analyzed.     

Si-doping effect on the enhanced hydrogen storage of single walled carbon nanotubes and graphene

We identified several parameters that correlate with the hydrogen physisorption energy and physicochemical properties of heteronuclear bonding in single-walled carbon nanotubes (SWCNT) and graphene. These parameters were used to find the most promising heteronuclear doping agents for SWCNTs and graphene for enhanced hydrogen storage capacity. Si-doping was showed to increase the amount of physisorbed hydrogen on such surfaces. Grand Canonical Ensemble Monte Carlo (GCMC) simulations showed that the hydrogen storage capacity of 10 at% Si-doped SWCNT (Si-CNT10) could reach a maximum of 2.5 wt%, almost twice the storage capacity of undoped SWCNTs, which were showed to reach a maximum capacity of 1.4 wt% at room temperature. To achieve this capacity, debundling effects of the uneven surfaces of Si-doped SWCNTs were found to be necessary. Similarly, 10 at% Si-doping on graphene (Si-GR10) was showed to increase the hydrogen storage capacity from 0.8 to 2.4 wt%.     

Hydrogen storage ability of porous carbon material fabricated from coffee bean wastes

The hydrogen storage ability at 298 and 77 K of porous carbon materials with microporous structures fabricated from coffee bean wastes through KOH activation was investigated regarding pore structure. The dependence of hydrogen storage ability on the pore structure of porous carbon materials was investigated at 298 and 77 K to clarify the storage mechanism of carbon materials. Hydrogen storage ability at 298 K was increased linearly with increasing of specific surface area increasing. The maximum amount of stored hydrogen was 0.6 wt.% on porous carbon material with 2070 m²/g specific surface area. The hydrogen storage ability at 77 K was 4.0 wt.% on the same sample. The hydrogen storage ability showed a linear relationship with the micro-pore volume size. These changes in the dependence of the hydrogen storage ability on pore size suggested that the storage configuration changed from two- to three-dimensional. The stored hydrogen densities in porous carbon materials calculated from these values were 5.7 and 69.6 mg/cm³ at 298 and 77 K, respectively. The change in density indicated that the state of stored hydrogen in porous carbon materials was filled up aggregational state, which is extremely close to the liquid state, and suggested the realizing of high hydrogen storage ability on carbon materials fabricated from agricultural waste.     

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.     

Helical confinement effects on hydrogen storage in double-walled carbon nanotubes

Molecular configurations are some of the important factors that strongly affect the hydrogen adsorption in carbon nanotubes (CNTs). A Quantum Molecular dynamics simulations are performed to study the adsorption isotherm of torsional double-walled carbon nanotubes (DWCNTs) filled with hydrogen molecules. The considered key factors that affect the hydrogen storage responses of the DWCNTs are the adsorption energy and the surface tension effect. Our simulated results show that 2-sided effect is observed and kinetic diameter of H₂ molecules is shortened approximately 4.11% under helical confinement. The results further reveal that the amounts of hydrogen storage wt% are computed at 77 K and found to be 1.77 wt% and 3.92 wt% for pristine and twisted-DWCNTs, respectively. Finally, it is shown that the adsorption heat, which reflects surface property, is twisted dependent.     

Effect of temperature on activated carbon nanotubes for hydrogen storage behaviors

In this work, activated multi-walled carbon nanotubes (Acti-MWNTs) with well-developed pore structures, a highly specific surface area, and higher hydrogen adsorption capacities due to CO₂ activation were prepared. The activation was performed at activation temperatures in the range of 500–1100 °C. The microstructure and crystallinity of the Acti-MWNTs were evaluated with a transmission electron microscope (TEM) and an FT-Raman spectrometer, respectively. The textural properties of the Acti-MWNTs were investigated by using a nitrogen gas sorption analyzer at 77 K. The hydrogen storage capacities of the Acti-MWNTs were investigated by BEL-HP at 298 K/100 bar. The hydrogen storage capacities of the Acti-MWNTs were enhanced to 0.78 wt.% by increasing activation temperatures to 900 °C, which resulted in the formation of a defective structure in the Acti-MWNTs. This result indicated that the CO₂ activation was one of the most effective methods to develop the textural properties, as well as to enhance the hydrogen storage capacities of MWNTs.     

Improved design of metal-organic frameworks for efficient hydrogen storage at ambient temperature: A multiscale theoretical investigation

A multiscale theoretical technique is used to examine the combination of different approaches for hydrogen storage enhancement in metal-organic frameworks at room temperature and high pressure by implementation lithium atoms in linkers. Accurate MP2 calculations are performed to obtain the hydrogen binding sites and parameters for the following grand canonical Monte Carlo (GCMC) simulations. GCMC calculations are employed to obtain the hydrogen uptake at different thermodynamic conditions. The results obtained demonstrate that the combination of different approaches can improve the hydrogen uptake significantly. The hydrogen content reaches 6.6 wt% at 300 K and 100 bar satisfying DOE storage targets (5.5 wt%).     

Molecular simulation on hydrogen storage properties of five novel covalent organic frameworks with the higher valency

With the methods of density functional theory (DFT) and molecular simulations, we have investigated the structural characteristics and hydrogen storage properties of five new reported boron-phosphorus cube based covalent organic frameworks (BP-COFs) with the higher valency. The structural parameters of five BP-COFs were researched by the numeric Monte Carlo (NMC) method, and the hydrogen adsorption properties were studied with grand canonical Monte Carlo (GCMC) simulations under the pressure of 0.1 bar–100 bar at both 77 K and 298 K. The results reveal that BP-COF-4 and BP-COF-5 possess the higher hydrogen adsorption capacities than BP-COF-1 to BP-COF-3 at both 77 K and 298 K. The possible methods to improve the H₂ adsorption properties of five BP-COFs are also proposed. We hope this study may provide some reference and inspiration for exploring new COFs with the higher valency as high-performance hydrogen storage materials in future.     

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.     

Spillover enhanced hydrogen uptake of Pt/Pd doped corncob-derived activated carbon with ultra-high surface area at high pressure

Corncob-derived activated carbon (CAC) was prepared by potassium hydroxide activation. The Pt/Pd-doped CAC samples were prepared by two-step reduction method (ethylene glycol reduction plus hydrogen reduction). The as-obtained samples were characterized by N₂-sorption, TEM and XRD. The results show the texture of CAC is varied after doping Pt/Pd. The Pd particles are easier to grow up than Pt particles on the surface of activated carbon. For containing Pt samples, the pore size distributions are different from original sample and Pd loaded sample. The hydrogen uptake results show excess hydrogen uptake capacity on the Pt/Pd-doped CAC samples are higher than pure CAC at 298 K, which should be attributed to hydrogen spillover effects. The 2.5%Pt and 2.5%Pd hybrid doped CAC sample shows the highest hydrogen uptake capacity (1.65 wt%) at 298 K and 180 bar, The particle size and distribution of Pt/Pd catalysts could play a crucial role on hydrogen uptake by spillover. The total hydrogen storage capacity analysis show that total H₂ storage capacities for all samples are similar, and spillover enhanced H₂ uptakes of metal-doped samples could not well support total H₂ storage capacity. The total pore volume of porous materials also is a key factor to affect total hydrogen storage capacity.     

Effects of cryomilling on the structures and hydrogen storage characteristics of multi-walled carbon nanotubes

Cryomilling was performed on multi-walled carbon nanotubes (MWCNTs) to investigate the effect of cyomilling on the structures and hydrogen storage characteristics of MWCNTs. Two milling speeds (300 and 700 rpm) and two milling times (2 and 6h) were applied in the cryomilling process. The results showed that the agglomeration of MWCNTs was significantly reduced, their lengths were shortened and the crystalline structure became amorphous at higher milling speed, whereas the milling time had no significant effect on the dispersibilities or structures of the MWCNTs. The hydrogen adsorption capacities of cryomilled MWCNTs at 700 rpm were improved by approximately 22% compared to that of unmilled MWCNTs due to the improvements in the specific surface area (17.4%) and pore volume (34.9%). Cryomilling is an effective method for increasing the surface area and pore volume, and macropores were transformed into mesopores, thereby enhancing the hydrogen storage capacity of the MWCNT surface. These results were confirmed by scanning and transmission electron microscopies, X-ray diffraction and Raman spectroscopic analysis.     

Grand canonical Monte Carlo simulations of hydrogen adsorption in carbon aerogels

Hydrogen storage plays a fundamental role in the future hydrogen energy system, and carbon aerogel is one of the most potential hydrogen storage materials because of its high gravimetric and volumetric density on hydrogen adsorption. In this paper, the amorphous structure of carbon, obtained by a numerical simulation process by using the molecular dynamic and Monte Carlo methods, as well as the primary unit method, was intercepted as a sphere structure for numerical annealing to build a carbon nanosphere, which serves as the basic unit to reconstruct the carbon aerogel's skeleton by the Diffusion Limited Cluster Aggregation (DLCA) method. The hydrogen adsorption in carbon aerogel was simulated by using the self-coding parallel grand canonical Monte Carlo (GCMC) method. The influences of particle diameter, density, temperature, pressure, and specific surface area on the hydrogen adsorbing capacity in carbon aerogel were analyzed in detail. The results showed that the carbon aerogel's hydrogen storage capacity with a specific surface area of 2680 m²/g could reach 4.52 wt % at 77 K and 3.0 MPa.     

Hydrogen storage in hybrid nanostructured carbon/palladium materials: Influence of particle size and surface chemistry

Hydrogen adsorption on porous materials is one of the possible methods proposed for hydrogen storage for transport applications. One way for increasing adsorption at room temperature is the inclusion of metal nanoparticles to increase hydrogen–surface interactions. In this study, ordered mesoporous carbon materials were synthesized by replication of nanostructured mesoporous SBA-15 silica. The combination of different carbon precursors allowed to tailor the textural, structural and chemical properties of the materials. These carbons were used for the synthesis of hybrid nanostructured carbon/palladium materials with different sizes of metal nanoparticles. The hydrogen sorption isotherms were measured at 77 K and 298 K between 0.1 and 8 MPa. Hydrogen storage capacities strongly correlate with the textural properties of the carbon at 77 K. At room temperature, Pd nanoparticles enhance hydrogen storage capacity by reversible formation of hydride PdH_x and through the spillover mechanism. The hydrogen uptake depends on the combined influences of metal particle size and of carbon chemical properties. Carbons obtained from sucrose precursors lead to the hybrid materials with the highest storage capacities since they exhibits a large microporous volume and a high density of oxygenated surface groups.     

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.