Hydrogen adsorption on model adsorbents from the viewpoint of the theory of volumetric filling of micropores

Hydrogen adsorption on model microporous adsorbents with slit-shaped pores was calculated on the basis of Dubinin’s theory of volumetric filling of micropores using the property of linearity of adsorption isosters. Model adsorbents with micropore widths of 0.5, 0.9, and 1.2 nm obtained by the successive exclusion of one, two, and three layers of hexagonal carbon in the crystalline lattice of graphite were used. Hydrogen adsorption was calculated in the structures with single-layer and two-layer carbon walls at temperatures 20, 33, 77, 200, 300, and 400 K and pressures up to 20 MPa. The maximal hydrogen desorption for the AU structure (1:3) with the pressure drop from 20 to 0.1 MPa was 8 wt.% at 200K. The parameters of the porous adsorbent structure were calculated.     

Hydrogen adsorption on nanoporous carbon adsorbents prepared from furaldehyde by thermochemical synthesis

Hydrogen adsorption on two samples of active carbon (FAS) produced from furaldehyde by the thermochemical synthesis method is investigated. Maximum hydrogen adsorption on these active carbons at hydrogen boiling temperature of 20.38 K and a pressure of 0.101 MPa is calculated in terms of the theory of the volume filling of micropores. Hydrogen adsorption on FAS-1-05 active carbon at temperatures of 77, 196, and 300 K and pressures of 7 and 20 MPa is calculated using the condition of linear isosteres. The calculated data are compared with the experimental results obtained for the same adsorbent at temperatures of 77 and 293 K and pressures below 5.1 and 16.1 MPa, respectively. The maximum adsorption value of hydrogen on FAS-1-05 amounts to 6.2 wt % at 5.1 MPa and 77 K.     

Hydrogen adsorption on model adsorbents in terms of volume filling of micropores: II. Hydrogen adsorption in the space between Single-Wall carbon nanotubes

Hydrogen adsorption in the space between Single-Wall carbon nanotubes arranged to form triangular packages is calculated at temperatures of 20–400 K in terms of the Dubinin theory of volume filling of micropores using the linearity of adsorption isosteres. Based on the data obtained, porous structure parameters are established that can be applied for hydrogen accumulation at pressures below 20 MPa and temperatures of 77–400 K.     

Thermodynamics of hydrogen adsorption in slit-like carbon nanopores at 77 K. Classical versus path-integral Monte Carlo simulations

Hydrogen in slit-like carbon nanopores at 77 K represents a quantum fluid in strong confinement. We have used path-integral grand canonical Monte Carlo and classical grand canonical Monte Carlo simulations for the investigation of the "quantumness" of hydrogen at 77 K adsorbed in slit-like carbon nanopores up to 1 MPa. We find that classical simulations overpredict the hydrogen uptake in carbon nanopores due to neglect of the quantum delocalization. Such disagreement of both simulation methods depends on the slit-like carbon pore size. However, the differences between the final uptakes of hydrogen computed from both classical and quantum simulations are not large due to a similar effective size of quantum/classical hydrogen molecules in carbon nanospaces. For both types of molecular simulations, the volumetric density of stored energy in optimal carbon nanopores exceeds 6.4 MJ dm(-3) (i.e., 45 kg m(-3); Department of Energy target for 2010). In contrast to the hydrogen adsorption isotherms, we found a large reduction of isosteric enthalpy of adsorption computed from the quantum Feynman's path-integral simulations in comparison to the classical values at 77 K and pressures up to 1 MPa. Depression of the quantum isosteric enthalpy of adsorption depends on the slit-like carbon pore size. For the narrow pores (pore width H in [0.59-0.7] nm), the reduction of the quantum isosteric enthalpy of adsorption at zero coverage is around 50% in comparison to the classical one. We observed new phenomena called, by us, the quantum confinement-inducing polymer shrinking. In carbon nanospaces, the quantum cyclic polymers shrink, in comparison to its bulk-phase counterpart, due to a strong confinement effect. At considered storage conditions, this complex phenomenon depends on the size of the slit-like carbon nanopore and the density of hydrogen volumetric energy. For the smallest nanopores and a low density of hydrogen volumetric energy, the reduction of the polymer effective size is the highest, whereas an increase of the pore size and the density of hydrogen volumetric energy causes the polymer swelling up to a value slightly below the one computed from the bulk phase. Quantum confinement-inducing polymer shrinking is of great importance for realizing the potential of quantum molecular sieves.     

Gas adsorption and storage in metal-organic framework MOF-177

Gas adsorption experiments have been carried out on a zinc benzenetribenzoate metal-organic framework material, MOF-177. Hydrogen adsorption on MOF-177 at 298 K and 10 MPa gives an adsorption capacity of approximately 0.62 wt %, which is among the highest hydrogen storage capacities reported in porous materials at ambient temperatures. The heats of adsorption for H2 on MOF-177 were -11.3 to -5.8 kJ/mol. By adding a H2 dissociating catalyst and using our bridge building technique to build carbon bridges for hydrogen spillover, the hydrogen adsorption capacity in MOF-177 was enhanced by a factor of approximately 2.5, to 1.5 wt % at 298 K and 10 MPa, and the adsorption was reversible. N2 and O2 adsorption measurements showed that O2 was adsorbed more favorably than N2 on MOF-177 with a selectivity of approximately 1.8 at 1 atm and 298 K, which makes MOF-177 a promising candidate for air separation. The isotherm was linear for O2 while being concave for N2. Water vapor adsorption studies indicated that MOF-177 adsorbed up to approximately 10 wt % H2O at 298 K. The framework structure of MOF-177 was not stable upon H2O adsorption, which decomposed after exposure to ambient air in 3 days. All the results suggested that MOF-177 could be a potentially promising material for gas separation and storage applications at ambient temperature (under dry conditions or with predrying).     

Hydrogen adsorption on functionalized nanoporous activated carbons

There is considerable interest in hydrogen adsorption on carbon nanotubes and porous carbons as a method of storage for transport and related energy applications. This investigation has involved a systematic investigation of the role of functional groups and porous structure characteristics in determining the hydrogen adsorption characteristics of porous carbons. Suites of carbons were prepared with a wide range of nitrogen and oxygen contents and types of functional groups to investigate their effect on hydrogen adsorption. The porous structures of the carbons were characterized by nitrogen (77 K) and carbon dioxide (273 K) adsorption methods. Hydrogen adsorption isotherms were studied at 77 K and pressure up to 100 kPa. All the isotherms were Type I in the IUPAC classification scheme. Hydrogen isobars indicated that the adsorption of hydrogen is very temperature dependent with little or no hydrogen adsorption above 195 K. The isosteric enthalpies of adsorption at zero surface coverage were obtained using a virial equation, while the values at various surface coverages were obtained from the van't Hoff isochore. The values were in the range 3.9-5.2 kJ mol(-1) for the carbons studied. The thermodynamics of the adsorption process are discussed in relation to temperature limitations for hydrogen storage applications. The maximum amounts of hydrogen adsorbed correlated with the micropore volume obtained from extrapolation of the Dubinin-Radushkevich equation for carbon dioxide adsorption. Functional groups have a small detrimental effect on hydrogen adsorption, and this is related to decreased adsorbate-adsorbent and increased adsorbate-adsorbate interactions.     

Adjustable structure transition and improved gases (H2, CO2) adsorption property of metal-organic framework MIL-53 by encapsulation of BNHx

The structure transition of flexible MOF (MIL-53) can be adjusted by confinement of BNH(x) into MIL-53 channels. Hydrogen and carbon dioxide adsorption properties are also improved by incorporating BNH(x). At 77 K and 1 atm pressure hydrogen storage capacity can reach 2.0 wt% and CO(2) adsorption capacity is 4.5 mmol g(-1) at 273 K 1 atm.     

Zeolite-templated carbon materials for high-pressure hydrogen storage

Zeolite-templated carbon (ZTC) materials were synthesized, characterized, and evaluated as potential hydrogen storage materials between 77 and 298 K up to 30 MPa. Successful synthesis of high template fidelity ZTCs was confirmed by X-ray diffraction and nitrogen adsorption at 77 K; BET surface areas up to ~3600 m(2) g(-1) were achieved. Equilibrium hydrogen adsorption capacity in ZTCs is higher than all other materials studied, including superactivated carbon MSC-30. The ZTCs showed a maximum in Gibbs surface excess uptake of 28.6 mmol g(-1) (5.5 wt %) at 77 K, with hydrogen uptake capacity at 300 K linearly proportional to BET surface area: 2.3 mmol g(-1) (0.46 wt %) uptake per 1000 m(2) g(-1) at 30 MPa. This is the same trend as for other carbonaceous materials, implying that the nature of high-pressure adsorption in ZTCs is not unique despite their narrow microporosity and significantly lower skeletal densities. Isoexcess enthalpies of adsorption are calculated between 77 and 298 K and found to be 6.5-6.6 kJ mol(-1) in the Henry's law limit.     

钾掺杂多壁纳米碳管储氢性能研究

使用自制的钴催化裂解碳氢气法制备多壁纳米碳管,并对其进行退火、掺杂等一系列预处理,然后使用高压高纯氢源,在中压(12 MPa)和室温条件下,进行钾掺杂多壁纳米碳管的储氢性能实验.结果表明:预处理对纳米碳管的储氢性能有很大影响.实验条件下,经过氮气退火,并在1.0 mol/L硝酸钾溶液中掺杂的多壁纳米碳管吸氢量最大(H/C质量分数为3.2%).上述样品在室温下的放氢量一般不超过其吸氢量的50.8%.     

Hydrogen storage in low silica type X zeolites

Low silica type X zeolites (LSX, Si/Al = 1) fully exchanged by alkali-metal cations (Li(+), Na(+), and K(+)) were studied for their hydrogen storage capacities. Hydrogen adsorption isotherms were measured separately at 77 K and <1 atm, and at 298 K and <10 MPa. It was found that the hydrogen adsorption capacity of LSX zeolite depended strongly on the cationic radius and the density of the cations that are located on the exposed sites. The interaction energies between H(2) and the cations follow the order Li(+) > Na(+) > K(+), as predicted based on the ionic radii. Oxygen anions on zeolite framework were minor adsorption sites. Li-LSX had an H(2) capacity of 1.5 wt % at 77 K and 1 atm, and a capacity of 0.6 wt % at 298 K and 10 MPa, among the highest of known sorbents. The hydrogen capacity in LSX zeolite by bridged hydrogen spillover was also investigated. A simple and effective technique was employed to build carbon bridges between the H(2) dissociation catalyst and the zeolite to facilitate spillover of hydrogen atoms. Thus, the hydrogen storage capacity of Li-LSX zeolite was enhanced to 1.6 wt % (by a factor of 2.6) at 298 K and 10 MPa. This is by far the highest hydrogen storage capacity obtained on a zeolite material at room temperature. Furthermore, the adsorption rates were fast, and the storages were shown to be fully reversible and rechargeable. Further optimization of the bridge building technique would lead to an additional enhancement of hydrogen storage.     

High-pressure phase studies on fluid mixtures of low-volatile organic substances with supercritical carbon dioxide

Two high-pressure phase equilibrium cells working according to the analytical method in the temperature range 300 to 450 K and up to 200 MPa have been developed. In the first cell p,T,x,y equilibrium data can be determined by sampling and GC analysis. With this cell the gas-liquid phase behaviour of the ternary systems carbon dioxide + tridecane + hexadecane and carbon dioxide + tridecane + 1-hexadecanol were determined at 423.4 K and between 8 and 35 MPa. For the second apparatus a spectroscopic high-pressure cell fitted with two pairs of sapphire windows was developed. Molar absorptivities are obtained from calibration runs in the homogeneous region. Gasliquid phase equilibria in the system decane + CO₂ were investigated from 342.8 to 400.2 K and between 10 and 20 MPa; here absorption data were measured in the NIR region.     

Hydrogen adsorption measurements and modeling on metal-organic frameworks and single-walled carbon nanotubes

Hydrogen adsorption measurements on Al-, Cr-, and Zn-based metal-organic frameworks (MOFs) and single-walled carbon nanotubes (SWNTs) are presented. The measurements were performed at temperatures ranging from 77 to 300 K and pressures up to 50 atm using a volumetric approach. The maximum excess adsorption at 77 K ranges from 2.3 to 3.9 wt % for the MOFs and from 1.5 to 2.5 wt % for the SWNTs. These values are reached at pressures below 40 atm. At room temperature and 40 atm, modest amounts of hydrogen are adsorbed (<0.4 wt %). A Dubinin-Astakhov (DA) approach is used to investigate the measured adsorption isotherms and to retrieve energetic and structural parameters. The adsorption enthalpy averaged over filling is about 2.9 kJ/mol for the MOF-5 and about 3.6-4.2 kJ/mol for SWNTs.     

DFT-based prediction of high-pressure H2 adsorption on porous carbons at ambient temperatures from low-pressure adsorption data measured at 77 K

Hydrogen adsorption isotherms were measured both at cryogenic temperatures below 1 atm and at ambient temperature at high pressures, up to 90 atm, on selected porous carbons with various pore structures. The nonlocal density functional theory (NLDFT) model was used to calculate the pore size distributions (PSDs) of the carbons, from H2 adsorption isotherms measured at 77 K, and then to predict H2 adsorption on these carbons at 87 and 298 K. An excellent agreement between the predicted and measured data was obtained. Prior to analyzing the porous carbons, the solid-fluid interaction parameters used in the NLDFT model were derived from H2 adsorption data measured at 77 K on nonporous carbon black. The results show that the NLDFT model with appropriate parameters may be a useful tool for optimizing carbon pore structures and designing adsorption systems for hydrogen storage applications.     

Adsorption of gases on layered silicates at high pressures

Equilibrium adsorption of nitrogen, carbon dioxide, and argon was examined on the sodium and pyridinium forms of montmorillonite and on the hydrogen form of bentonite. The measurements were carried out at 303, 343, 373, and 400 K over pressure ranges of 0.1–90 MPa (Ar and N₂) and 0.1–6 MPa (CO₂). The amount of nitrogen vapor adsorbed was determined at 77 K and pressures from 0 to 0.1 MPa. The porous structure parameters of the studied samples were determined using adsorption isotherms of nitrogen, argon, and carbon dioxide vapors. At elevated temperatures and pressures >10 MPa, Ar and N₂ adsorption processes on the Na-form of montmorillonite and Ar adsorption on bentonite are activated, since the amounts of the gases adsorbed and adsorption volumes increase with temperature. No activated adsorption is observed for carbon dioxide adsorption on these adsorbents. A comparison of the excess adsorption isotherms of gases on the Py-form of montmorillonite and H-form of bentonite shows that adsorption in micropores predominates for the Py-form of montmorillonite, whereas for the Na-form of bentonite and H-form of bentonite adsorption occurs mainly in meso- and macropores.     

氢气在单壁碳纳米管束的吸附的密度泛函研究

作者利用密度泛函理论（DFT）计算了氢气在单壁碳纳米管束（SWNTs)中管内 和管间的吸附。考察了温度,孔径以及压力对吸附的分子数密度,重量百分比,单 位体积储存能力以及超额吸附量的影响。DFT计算发现,较大的孔径有利于氢气在 SWNTs中的吸附且氢气在管隙中的吸附不可忽略。计算表明在77 K和6 MPa时,氢气 在2.719 mm的SWNTs的总的吸附的重量百分比分别可达到13.2 wt%,这约是美国能 源部（DOE）目标值的两倍,而单位体积储存能力在DOE目标值附近,而在300 K和 6 MPa时,氢气在2.719 nm的SWNTs的总的吸附的重量百分比仅为1.5 wt%。通过实 验结果与计算结果的比较表明,密度泛函理论的计算结果支持SWNTs有较高的吸附 储氢能力的实验结论。     

Adsorption of hydrogen on nanoporous carbon adsorbents

Four samples of active carbons with specific micropore volumes of 0.4—1.33 cm³g^-1 at 77 K and pressures up to 5 MPa were used to study hydrogen adsorption. The highest amount of of hydrogen adsorbed on these active carbons at the boiling point 20.38 K and pressure 0.101 MPa was calculated by methods derived from the theory of volumetric filling of micropores (TVFM). The adsorbent FAS-1-05 prepared by the liquid-phase polymerization of furfurol was shown to have the highest adsorption capacity. The amounts of hydrogen adsorbed on FAS-1-05 at temperatures 77, 196, and 300 K and pressures 7 and 20 MPa were calculated using the TVFM methods with allowance for linearity of the isosters. The results were compared with the experimental values obtained at 77 K and pressure below 5.1 MPa and at 293 K and pressures up to 16.1 MPa. The highest amounts of hydrogen adsorbed (6.2 wt.% for the adsorbent FAS-1-05) were obtained under pressures below 5.1 MPa and at 77 K.     

Molecular insight into the high selectivity of double-walled carbon nanotubes

Combining experimental knowledge with molecular simulations, we investigated the adsorption and separation properties of double-walled carbon nanotubes (DWNTs) against flue/synthetic gas mixture components (e.g. CO(2), CO, N(2), H(2), O(2), and CH(4)) at 300 K. Except molecular H(2), all studied nonpolar adsorbates assemble into single-file chain structures inside DWNTs at operating pressures below 1 MPa. Molecular wires of adsorbed molecules are stabilized by the strong solid-fluid potential generated from the cylindrical carbon walls. CO(2) assembly is formed at very low operating pressures in comparison to all other studied nonpolar adsorbates. The adsorption lock-and-key mechanism results from perfect fitting of rod-shaped CO(2) molecules into the cylindrical carbon pores. The enthalpy of CO(2) adsorption in DWNTs is very high and reaches 50 kJ mol(-1) at 300 K and low pore concentrations. In contrast, adsorption enthalpy at zero coverage is significantly lower for all other studied nonpolar adsorbates, for instance: 35 kJ mol(-1) for CH(4), and 14 kJ mol(-1) for H(2). Applying the ideal adsorption solution theory, we predicted that the internal pores of DWNTs have unusual ability to differentiate CO(2) molecules from other flue/synthetic gas mixture components (e.g. CO, N(2), H(2), O(2), and CH(4)) at ambient operating conditions. Computed equilibrium selectivity for equimolar CO(2)-X binary mixtures (where X: CO, N(2), H(2), O(2), and CH(4)) is very high at low mixture pressures. With an increase in binary mixture pressure, we predicted a decrease in equilibrium separation factor because of the competitive adsorption of the X binary mixture component. We showed that at 300 K and equimolar mixture pressures up to 1 MPa, the CO(2)-X equilibrium separation factor is higher than 10 for all studied binary mixtures, indicating strong preference for CO(2) adsorption. The overall selective properties of DWNTs seem to be superior, which may be beneficial for potential industrial applications of these novel carbon nanostructures.     

Effect of expanded graphite lattice in exfoliated graphite nanofibers on hydrogen storage

A graphite exfoliation technique, using intercalation of a concentrated sulfuric/nitric acid mixture followed by a thermal shock, has successfully exfoliated a herringbone graphite nanofiber (GNF). The exfoliated GNF retains the overall nanosized dimensions of the original GNF, with the exfoliation temperature determining the degree of induced defects, lattice expansion, and resulting microstructure. High-resolution transmission electron microscopy indicated that the fibers treated at an intermediate temperature of 700 degrees C for 2 min had dislocations in the graphitic structure and a 4% increase in graphitic lattice spacing to 3.5 A. The fibers treated at 1000 degrees C for 36 h were expanded along the fiber axis, with regular intervals of graphitic and amorphous regions ranging from 0.5 to >50 nm in width. The surface area of the starting material was increased from 47 m(2)/g to 67 m(2)/g for the 700- degrees C treatment and to 555 m(2)/g for the 1000- degrees C treatment. Hydrogen uptake measurements at 20 bar indicate that the overall hydrogen uptake and operative adsorption temperature are sensitive to the structural variations and graphitic spacing. The increased surface area after the 1000- degrees C treatment led to a 1.2% hydrogen uptake at 77 K and 20 bar, a 3-fold increase in hydrogen physisorption of the starting material. The uptake of the 700- degrees C-treated material had a 0.29% uptake at 300 K and 20 bar; although low, this was a 14-fold uptake over the starting material and higher than other commonly used pretreatment methods that were tested in parallel. These results suggest that selective exfoliation of a nanofiber is a means by which to control the relative binding energy of the hydrogen interaction with the carbon structure and thus vary the operative adsorption temperature.     

高比表面活性碳微球分离H2中少量CO2

以实验数据为依据, 结合双Langmuir模型研究了用高比表面活性碳微球材料分离H2中少量CO2的行为. 在实验中, 用高精度的IGA-003重力吸附仪测定了温度为298、273 和268 K, 压力在0-1.8 MPa范围内CO2、H2及n(CO2):n(H2)=1:9混合物在活性碳微球中的吸附等温线. 比较不同吸附模型的计算结果与实验数据, 结果表明, 双Langmuir模型与实验结果拟合得较好; 而且通过结合理想吸附溶液理论, 该模型可以准确地计算不同的混合物体系(包括H2-CO2体系)的吸附量和吸附选择性. 利用该模型求解了不同温度下各组分的分吸附量, 得到了CO2的吸附选择性;在268 K和1.7 MPa下, CO2的吸附选择性可达到73.4, 表明活性碳微球是一种优秀的吸附H2中少量CO2的材料.     

Gibbs系综Monte Carlo模拟甲烷的吸附平衡

在263、298和313 K下,对甲烷在1.91 nm的活性炭孔中的吸附平衡进行了Gibbs系综Monte Carlo(GEMC)模拟的研究.改进了GEMC方法,使之可用于模拟指定压力下的吸附平衡.通过改进的GEMC模拟,得到了在1.91 nm的活性炭中甲烷在263、298和313 K时的吸附等温线;发现263 K时的超额吸附量要大于298 K、313 K时的超额吸附量; 且不同温度下的超额吸附等温线均存在一最大超额吸附.263 K时,超额吸附量在5.0 MPa时出现最大值;而298 K、313 K时超额吸附量则在7.0 MPa时出现最大值.此工作为不同温度下天然气吸附存贮过程的开发及设计提供了依据.