Hydrogen adsorption in transition metal carbon nano-structures

Templated microporous carbons were synthesized from metal impregnated zeolite Y templates. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to characterize morphology and structure of the generated carbon materials. The surface area, micro- and meso-pore volumes, as well as the pore size distribution of all the carbon materials were determined by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. All the hydrogen adsorption isotherms were Type 1 and reversible, indicating physisorption at 77 K. Most templated carbons show good hydrogen storage with the best sample Rh-C having surface area 1817 m²/g and micropore volume 1.04 cm³/g, achieving the highest as 8.8 mmol/g hydrogen storage capacity at 77 K, 1 bar. Comparison between activated carbons and synthesized templated carbons revealed that the hydrogen adsorption in the latter carbon samples occurs mainly by pore filling and smaller pores of sizes around 6 Å to 8 Å are filled initially, followed by larger micropores. Overall, hydrogen adsorption was found to be dependent on the micropore volume as well as the pore-size, larger micropore volumes showing higher hydrogen adsorption capacity.     

Enhanced hydrogen storage capacity of high surface area zeolite-like carbon materials

We report the synthesis of zeolite-like carbon materials that exhibit well-resolved powder XRD patterns and very high surface area. The zeolite-like carbons are prepared via chemical vapor deposition (CVD) at 800 or 850 degrees C using zeolite beta as solid template and acetonitrile as carbon precursor. The zeolite-like structural ordering of the carbon materials is indicated by powder XRD patterns with at least two well-resolved diffraction peaks and TEM images that reveal well-ordered micropore channels. The carbons possess surface area of up to 3200 m2/g and pore volume of up to 2.41 cm3/g. A significant proportion of the porosity in the carbons (up to 76% and 56% for surface area and pore volume, respectively) is from micropores. Both TEM and nitrogen sorption data indicate that porosity is dominated by pores of size 0.6-0.8 nm. The carbon materials exhibit enhanced (and reversible) hydrogen storage capacity, with measured uptake of up to 6.9 wt % and estimated maximum of 8.33 wt % at -196 degrees C and 20 bar. At 1 bar, hydrogen uptake capacity as high as 2.6 wt % is achieved. Isosteric heat of adsorption of 8.2 kJ/mol indicates a favorable interaction between hydrogen and the surface of the carbons. The hydrogen uptake capacity observed for the zeolite-like carbon materials is among the highest ever reported for carbon (activated carbon, mesoporous carbon, CNTs) or any other (MOFs, zeolites) porous material.     

Influence of surface treatments on micropore structure and hydrogen adsorption behavior of nanoporous carbons

The scope of this work was to control the pore sizes of porous carbons by various surface treatments and to investigate the relation between pore structures and hydrogen adsorption capacity. The effects of various surface treatments (i.e., gas-phase ozone, anodic oxidation, fluorination, and oxygen plasma) on the micropore structures of porous carbons were investigated by N(2)/77 K isothermal adsorption. The hydrogen adsorption capacity was measured by H(2) isothermal adsorption at 77 K. In the result, the specific surface area and micropore volume of all of the treated samples were slightly decreased due to the micropore filling or pore collapsing behaviors. It was also found that in F(2)-treated carbons the center of the pore size distribution was shifted to left side, meaning that the average size of the micropores decreased. The F(2)- and plasma-treated samples showed higher hydrogen storage capacities than did the other samples, the F(2)-treated one being the best, indicating that the micropore size of the porous carbons played a key role in the hydrogen adsorption at 77 K.     

Preparation and characterization of ordered porous carbons for increasing hydrogen storage behaviors

We prepared ordered porous carbons (PCs) by using a replication method that had well-organized mesoporous silica as a template with various carbonization temperatures in order to investigate the possibility of energy storage materials. The microstructure and morphologies of the samples are characterized by XRD, TEM, and FT-Raman spectroscopy. N₂ adsorption isotherms are analyzed by the t-plot method, as well as the BET and the H–K method in order to characterize the specific surface area, pore volume, and pore size distribution of the samples, respectively. The capacity of the hydrogen adsorption of the samples is evaluated by BEL-HP at 77 K and 1 bar. From the results, we are able to confirm that the synthesis of the samples can be accurately governed by the carbonization temperature, which is one of the effective parameters for developing the textural properties of the carbon materials, which affects the behaviors of the hydrogen storage.     

有序中孔炭的电化学储氢性能

将蔗糖、聚环氧乙烯-聚环氧丙烯-聚环氧乙烯三嵌段共聚物和硅源构成的复合物进行预炭化、炭化和除硅处理合成出有序中孔炭, 采用XRD、TEM、HRTEM和N2吸脱附等手段对其进行表征, 并将有序中孔炭制成电极开展恒流充放电储氢性能研究. 结果显示, 具有较高比表面积(720 m2·g-1)和孔容(0.86 cm3·g-1)的有序中孔炭材料的电化学储氢容量为70.1 mAh·g-1, 高于具有相对较低比表面积(610 m2·g-1)和孔容(0.66 cm3·g-1)的有序中孔炭储氢容量(64.1 mAh·g-1). 通过与单壁碳纳米管电极(25.9 mAh·g-1)的对比, 表明有序中孔炭具有良好的电化学储氢性能和更高的电化学活性.     

Preparation and hydrogen storage properties of zeolite-templated carbon materials nanocast via chemical vapor deposition: effect of the zeolite template and nitrogen doping

Carbon materials have been prepared using zeolite 13X or zeolite Y as template and acetonitrile or ethylene as carbon source via chemical vapor deposition (CVD) at 550-1000 degrees C. Materials obtained from acetonitrile at 750-850 degrees C (zeolite 13X) or 750-900 degrees C (zeolite Y) have high surface area (1170-1920 m(2)/g), high pore volume (0.75-1.4 cm(3) g(-1)), and exhibit some structural ordering replicated from the zeolite templates. Templating with zeolite Y generally results in materials with higher surface area. High CVD temperature (> or =900 degrees C) results in low surface area materials that have significant proportions of graphitic carbon and no zeolite-type structural ordering. The nitrogen content of the samples derived from acetonitrile varies between 5 and 8 wt %. When ethylene is used as a carbon precursor, high surface area (800-1300 m(2)/g) materials are only obtained at lower CVD temperature (550-750 degrees C). The ethylene-derived carbons retain some zeolite-type pore channel ordering but also exhibit significant levels of graphitization even at low CVD temperature. In general, the carbon materials retain the particle morphology of the zeolite templates, with solid-core particles obtained at 750-850 degrees C while hollow shells are generated at higher CVD temperature (> or =900 degrees C). We observed hydrogen uptake of up to 4.5 wt % and 45 g H(2)/L (volumetric density) at -196 degrees C and 20 bar for the carbon materials. The hydrogen uptake was found to be dependent on surface area and was therefore influenced by the choice of zeolite template and carbon source. Zeolite Y-templated N-doped carbons had the highest hydrogen uptake capacity. Gravimetric and volumetric methods gave similar uptake capacity at 1 bar (i.e., 1.6 and 2.0 wt % for zeolite 13X and Y-templated N-doped carbons, respectively). Our findings show that zeolite-templated carbons are attractive for hydrogen storage and highlight the potential benefits of functionalization (nitrogen-doping).     

Ordered porous carbon with tailored pore size for electrochemical hydrogen storage application

Ordered porous carbon with tailored pore size represents an innovative concept in electrochemical hydrogen storage. This work deals with physical characteristics and electrochemical hydrogen storage behavior of the ordered porous carbons with well-tailored pore size, synthesized by a replica technique using hexagonal mesoporous silica as templates. By using a mixture of two surfactants (HTAB and C16EO8) at different ratios, it is possible to control the wall thickness of silica and, consequently, the pore diameter of carbons within a narrow range of 2.1-2.8 nm. In addition, highly developed ultramicroporosity (pore size smaller than 0.7 nm), which plays a predominant role in hydrogen storage, can be produced in the ordered porous carbons. A discharge capacity of up to 527 mAh/g (corresponding to 1.95 wt % hydrogen storage) has been achieved in 6 M KOH for the ordered porous carbon. Furthermore, the ordered porous carbons also possess excellent capacity retainability after charge-discharge cycles and rate capability.     

Optimization of slitlike carbon nanopores for storage of hythane fuel at ambient temperatures

Carbons with slitlike pores can serve as effective host materials for storage of hythane fuel, a bridge between the petrol combustion and hydrogen fuel cells. We have used grand canonical Monte Carlo simulation for the modeling of the hydrogen and methane mixture storage at 293 K and pressure of methane and hydrogen mixture up to 2 MPa. We have found that these pores serve as efficient vessels for the storage of hythane fuel near ambient temperatures and low pressures. We find that, for carbons having optimized slitlike pores of size H congruent with 7 A (pore width that can accommodate one adsorbed methane layer), and bulk hydrogen mole fraction >or=0.9, the volumetric stored energy exceeds the 2010 target of 5.4 MJ dm(-3) established by the U.S. FreedomCAR Partnership. At the same condition, the content of hydrogen in slitlike carbon pores is approximately = 7% by energy. Thus, we have obtained the composition corresponding to hythane fuel in carbon nanospaces with greatly enhanced volumetric energy in comparison to the traditional compression method. We proposed the simple system with added extra container filled with pure free/adsorbed methane for adjusting the composition of the desorbed mixture as needed during delivery. Our simulation results indicate that light slit pore carbon nanomaterials with optimized parameters are suitable filling vessels for storage of hythane fuel. The proposed simple system consisting of main vessel with physisorbed hythane fuel, and an extra container filled with pure free/adsorbed methane will be particularly suitable for combustion of hythane fuel in buses and passenger cars near ambient temperatures and low pressures.     

Synthesis of zeolite-casted microporous carbons and their hydrogen storage capacity

Zeolite-casted microporous carbons (ZMiPCs) were synthesized using the replica casting method. The ZMiPC were also treated chemically by H(3)PO(4) (A-ZMiPC) or KOH (B-ZMiPC) impregnation, to investigate the effect of the acceptor-donor interaction on the hydrogen storage behaviors. The presence of functional groups of the modified ZMiPC surfaces was confirmed by X-ray photoelectron spectroscopy. The total acidity of the carbon surfaces was determined using the Boehm titration method. The microstructure was characterized by X-ray diffraction. The N(2)/77K adsorption/desorption isotherms were analyzed to characterize specific surface area, pore volume, and pore size distribution of the samples. The capacity of hydrogen adsorption was evaluated using a pressure-composition-temperature apparatus at 298K/100bar. From these results, the specific surface areas and micropore volume of ZMiPC increased more than two fold compared to the zeolite template. Meanwhile, the textural properties of A-ZMiPC and B-ZMiPC were decreased by the chemical treatments. Consequently, the largest hydrogen storage was obtained on A-ZMiPC, even though their textural properties had decreased, due to a charge induced dipole interaction between the modified carbon surface and hydrogen molecules.     

Characterization of pore structure in metal-organic framework by small-angle X-ray scattering

MOF-5-like crystals were studied by small-angle X-ray scattering (SAXS) to reveal, both quantitatively and qualitatively, their real structural details, including pore surface characteristics, pore shape, size distribution, specific surface area (SSA), spatial distribution, and pore-network structure. A combined SAXS and wide-angle X-ray scattering (WAXS) experiment was conducted to investigate the variation of the pore structure with the MOF-5 crystalline phase produced at different cooling rates. The SSA of the MOF-5 crystals synthesized herein spanned a broad range from approximately 3100 to 800 m2/g. The real pore structures were divided into two regimes. In regime I the material consisted mainly of micropores of radius approximately 8 A as well as mesopores of radius 120 approximately 80 A. The structure in regime II was a fractal network of aggregated mesopores with radius >or=32 A as the monomer, reducing SSA and hydrogen uptake capacity at room temperature. The two regimes can be manipulated by controlling the synthesis parameters. The concurrent evolution of pore structure and crystalline phase during heating for solvent removal was also revealed by the in-situ SAXS/WAXS measurement. The understanding of the impact of the real pore structure on the properties is important to establish a favorable synthetic approach for markedly improving the hydrogen storage capacity of MOF-5.     

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.     

H2 storage in carbon materials

In this work a series of commercial carbons with different structural and textural properties were characterised and evaluated for their application in hydrogen storage. The results showed that temperature has a greater influence on the storage capacity of carbons than pressure. The highest H₂ storage capacity at 298 K and 90 bar was 0.5 wt%, while at 77 K and atmospheric pressure it was 2.9 wt%. It is also showed that, in order to predict the hydrogen storage capacity of carbon material both at cryogenic and ambient temperature, the only use of BET surface area or total micropore volume obtained from N₂ adsorption isotherm may be insufficient, the characterization of the narrow microporosity is needed due to its high contribution to hydrogen adsorption capacity. The process involved in hydrogen storage in pure carbon materials seems to be physisorption. Morphological or structural characteristics have no influence, at least on gravimetric storage capacity.     

Storage of hydrogen at 303 K in graphite slitlike pores from grand canonical Monte Carlo simulation

Grand canonical Monte Carlo (GCMC) simulations were used for the modeling of the hydrogen adsorption in idealized graphite slitlike pores. In all simulations, quantum effects were included through the Feynman and Hibbs second-order effective potential. The simulated surface excess isotherms of hydrogen were used for the determination of the total hydrogen storage, density of hydrogen in graphite slitlike pores, distribution of pore sizes and volumes, enthalpy of adsorption per mole, total surface area, total pore volume, and average pore size of pitch-based activated carbon fibers. Combining experimental results with simulations reveals that the density of hydrogen in graphite slitlike pores at 303 K does not exceed 0.014 g/cm(3), that is, 21% of the liquid-hydrogen density at the triple point. The optimal pore size for the storage of hydrogen at 303 K in the considered pore geometry depends on the pressure of storage. For lower storage pressures, p < 30MPa, the optimal pore width is equal to a 2.2 collision diameter of hydrogen (i.e., 0.65 nm), whereas, for p congruent with 50MPa, the pore width is equal to an approximately 7.2 collision diameter of hydrogen (i.e., 2.13 nm). For the wider pores, that is, the pore width exceeds a 7.2 collision diameter of hydrogen, the surface excess of hydrogen adsorption is constant. The importance of quantum effects is recognized in narrow graphite slitlike pores in the whole range of the hydrogen pressure as well as in wider ones at high pressures of bulk hydrogen. The enthalpies of adsorption per mole for the considered carbonaceous materials are practically constant with hydrogen loading and vary within the narrow range q(st) congruent with 7.28-7.85 kJ/mol. Our systematic study of hydrogen adsorption at 303 K in graphite slitlike pores gives deep insight into the timely problem of hydrogen storage as the most promising source of clean energy. The calculated maximum storage of hydrogen is equal to approximately 1.4 wt %, which is far from the United States Department of Energy (DOE) target (i.e., 6.5 wt %), thus concluding that the total storage amount of hydrogen obtained at 303 K in graphite slitlike pores of carbon fibers is not sufficient yet.     

薄壁中孔碳材料的精细控制合成

利用γ-氧化铝为模板, 精细控制合成了一系列具有不同孔径的中孔碳材料. 在优化的条件下, 所得的碳材料具有孔径分布窄、比表面积高(>1000 m²·g^-1)、孔容大(最高3.82 cm³·g^-1)、中孔率高(>99%)的特点, 并且孔壁厚度仅有1-2个石墨层. 选用了三种不同来源的氧化铝为模板, 考察了模板与所得碳材料织构的相关性, 并提出用无序模板可控制备碳材料的机理. 即在碳包覆氧化铝的复合物前体中, 若碳层完整覆盖氧化铝表面并且足够强韧, 则所得碳材料可近似复制模板的孔结构, 并且碳材料的孔一部分由去除模板所生成, 另一部分来源于模板原有的孔. 据此模型对所得碳材料的孔容进行了理论计算, 其结果有力支持了上述机理.     

Hydrogen adsorption on microporous materials at ambient temperatures and pressures up to 50 MPa

High surface area microporous adsorbents are often proposed as potential hydrogen storage materials, although typically at 77?K and less than 5?MPa. In this study, we focus on conditions more suitable for automotive applications by investigating the storage capacities of microporous materials at 298?K and at pressures up to 50?MPa. In an effort to derive trends within and across material classes, we examined a wide range of materials with varying microstructures including the activated carbons AX-21, KUA-5, and MSC-30; a zeolite templated carbon; a hypercrosslinked polymer; and the Metal Organic Frameworks MOF-177, IRMOF-20, MIL-53, ZIF-8, and Cu₃(btc)₂. The peak excess adsorption of these materials ranged from 0.8–1.8?wt.%, although many did not reach their maximum capacity even at high pressures. However, the total volumetric storage gains over compressed hydrogen gas were quite low and, in many cases, negative. In addressing ambient temperature adsorption at significantly higher pressures than previously reported, our data confirms and extends the range of validity of several existing DFT calculations. Furthermore, our data suggest that, for both activated carbons and MOFs, factors other than specific surface area govern ambient temperature adsorption capacity. Contrary to some reports, the high fractions of sub-nanometer pores in some of the investigated MOFs did not appear to enhance the excess adsorption even at high pressures. For on-board applications with ambient temperature storage, significant enhancements to the attractive force at the materials’ surface are required, beyond merely increasing specific surface area, or for MOFs, tuning of pore sizes.     

The effects of preparation temperature on microstructure and electrochemical performance of calcium carbide-derived carbon

Calcium carbide-derived carbons (CCDCs) produced by chlorination of CaC₂ at various temperatures (400–800 °C) possess highly controllable microstructure and porosity, allowing them to serve as excellent electrode materials for the application of supercapacitor. This paper focused on the effect of pore size and specific surface area (SSA) of CCDC on its electrochemical behavior. Microstructure and micropore characteristics of CCDC were characterized by N₂ adsorption/desorption isotherms, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that SSA and average pore size increased with the increase of synthesis temperature from 400 °C to 600 °C, and then decreased when temperature reached to 800 °C. Meanwhile, a correlation between specific capacitance and SSA of micropores (less than 2 nm in diameter) has been studied. It has been found that the supercapacitor using the CCDC prepared at 600 °C as electrode material in 6 M KOH showed the maximum specific capacitance and energy density (53.61 F g^?1 and 7.08 W h kg^?1), outstanding rate capability, lower IR drop and 96 % retention of initial capacity over 5,000 cycles.     

Hypothetical high-surface-area carbons with exceptional hydrogen storage capacities: open carbon frameworks

A class of high-surface-area carbon hypothetical structures has been investigated that goes beyond the traditional model of parallel graphene sheets hosting layers of physisorbed hydrogen in slit-shaped pores of variable width. The investigation focuses on structures with locally planar units (unbounded or bounded fragments of graphene sheets), and variable ratios of in-plane to edge atoms. Adsorption of molecular hydrogen on these structures was studied by performing grand canonical Monte Carlo simulations with appropriately chosen adsorbent-adsorbate interaction potentials. The interaction models were tested by comparing simulated adsorption isotherms with experimental isotherms on a high-performance activated carbon with well-defined pore structure (approximately bimodal pore-size distribution), and remarkable agreement between computed and experimental isotherms was obtained, both for gravimetric excess adsorption and for gravimetric storage capacity. From this analysis and the simulations performed on the new structures, a rich spectrum of relationships between structural characteristics of carbons and ensuing hydrogen adsorption (structure-function relationships) emerges: (i) Storage capacities higher than in slit-shaped pores can be obtained by fragmentation/truncation of graphene sheets, which creates surface areas exceeding of 2600 m(2)/g, the maximum surface area for infinite graphene sheets, carried mainly by edge sites; we call the resulting structures open carbon frameworks (OCF). (ii) For OCFs with a ratio of in-plane to edge sites ≈1 and surface areas 3800-6500 m(2)/g, we found record maximum excess adsorption of 75-85 g of H(2)/kg of C at 77 K and record storage capacity of 100-260 g of H(2)/kg of C at 77 K and 100 bar. (iii) The adsorption in structures having large specific surface area built from small polycyclic aromatic hydrocarbons cannot be further increased because their energy of adsorption is low. (iv) Additional increase of hydrogen uptake could potentially be achieved by chemical substitution and/or intercalation of OCF structures, in order to increase the energy of adsorption. We conclude that OCF structures, if synthesized, will give hydrogen uptake at the level required for mobile applications. The conclusions define the physical limits of hydrogen adsorption in carbon-based porous structures.     

The study of controlling pore size on electrospun carbon nanofibers for hydrogen adsorption

Polyacrylonitrile (PAN)-based carbon nanofibers (CNFs) were prepared by using electrospinning method and heat treatment to get the media for hydrogen adsorption storage. Potassium hydroxide and zinc chloride activations were conducted to increase specific surface area and pore volume of CNFs. To investigate the relation between pore structure and the capacity of hydrogen adsorption, textural properties of activated CNFs were studied with micropore size distribution, specific surface area, and total pore volume by using BET (Brunauer-Emmett-Teller) surface analyzer apparatus and the capacity of hydrogen adsorption was evaluated by PCT (pressure-composition-temperature) hydrogen adsorption analyzer apparatus with volumetric method. The surface morphology of activated CNFs was observed by SEM (scanning electron microscope) images to investigate the surface change through activation. Even though specific surface area and total pore volume were important factors for increasing the capacity of hydrogen adsorption, the pore volume which has pore width (0.6-0.7 nm) was a much more effective factor than specific surface area and pore volume in PAN-based electrospun activated CNFs.     

A new method to determine pore size and its volume distribution of porous solids having known atomistic configuration

A simple method, based on Monte Carlo integration, is presented to derive pore size and its volume distribution for porous solids having known configuration of solid atoms. Because pores do not have any particular shape, it is important that we define the pore size in an unambiguous manner and the volume associated with each pore size. The void volume that we adopt is the one that is accessible to the center of mass of the probe particle. We test this new method with porous solids having well defined pores such as graphitic slit pores and carbon nanotubes, and then apply it to obtain the pore volume distribution of complex solids such as disordered solids, rectangular pores, defected graphitic pores, metal organic framework and zeolite.     

孔结构对活性炭吸附水溶液中铅离子的影响

选取三种表面化学性质相近的活性炭(AC),通过等温吸附实验考察活性炭对水溶液中铅离子的吸附性能,利用扫描电子显微镜(SEM)观察活性炭的表面微观形貌,通过低温(77 K)液氮吸附测定活性炭的比表面积和孔容,并分别以密度泛函理论(DFT)和Barrett-Joyner-Halenda (BJH)法计算微孔和中孔的孔径分布.结果表明:选用的三种活性炭AC1、AC2、AC3在比表面积和总孔容上呈依次下降的趋势,但表面开放孔均匀分布的AC2,具有最高的饱和吸附量,孔结构类似颗粒堆积孔的AC3,具有与表面开放孔分布集中的AC1相近的饱和吸附量;通过对孔结构与吸附量的关联分析可知,在活性炭吸附铅离子的过程中, 0.4-0.6 nm的孔是有效吸附孔, 10.5-20.6 nm、20.6-55.6 nm、5.2-10.5 nm三个区间的孔则会对吸附产生阻碍作用.