Distribution of carbon nanotube sizes from adsorption measurements and computer simulation

The method for the evaluation of the distribution of carbon nanotube sizes from the static adsorption measurements and computer simulation of nitrogen at 77 K is developed. We obtain the condensation/evaporation pressure as a function of pore size of a cylindrical carbon tube using Gauge Cell Monte Carlo Simulation (Gauge Cell MC). To obtain the analytical form of the relationships mentioned above we use Derjaguin-Broekhoff-deBoer theory. Finally, the pore size distribution (PSD) of the single-walled carbon nanohorns (SWNHs) is determined from a single nitrogen adsorption isotherm measured at 77 K. We neglect the conical part of an isolated SWNH tube and assume a structureless wall of a carbon nanotube. We find that the distribution of SWNH sizes is broad (internal pore radii varied in the range 1.0-3.6 nm with the maximum at 1.3 nm). Our method can be used for the determination of the pore size distribution of the other tubular carbon materials, like, for example, multiwalled or double-walled carbon nanotubes. Besides the applicable aspect of the current work the deep insight into the problem of capillary condensation/evaporation in confined carbon cylindrical geometry is presented. As a result, the critical pore radius in structureless single-walled carbon tubes is determined as being equal to three nitrogen collision diameters. Below that size the adsorption-desorption isotherm is reversible (i.e., supercritical in nature). We show that the classical static adsorption measurements combined with the proper modeling of the capillary condensation/evaporation phenomena is a powerful method that can be applied for the determination of the distribution of nanotube sizes.     

Adsorption Characteristics of Natural Erionite, Clinoptilolite and Mordenite Zeolites from Mexico

Nitrogen sorption properties inherent to some natural zeolites from Mexico, such as erionites, clinoptilolites and mordenites, are determined and compared with corresponding sorption properties of homologous synthetic or acid modified forms. The mineralogies of natural zeolites are determined by X-ray analysis. N₂ low-pressure hysteresis loops are displayed by some substrata while are absent in others; key factors for this phenomenon to occur are the micropore structure and the ion-exchange treatment to which the natural precursors are subjected. Argon sorption at 76 K on selected samples evidence further the strong adsorption and the pore blocking effects at pore necks in the zeolites.     

Adsorption Study of Methane on Activated Meso-carbon Microbeads by Density Functional Theory

A combined method of density functional theory (DFT) and statistics integral equation (SIE) for the determination of the pore size distribution (PSD) is developed based on the experimental adsorption data of nitrogen on activated mesocarbon microbead (AMCMB) at 77K. The pores of AMCMB are described as slit-shaped with PSD.Based on the PSD, methane adsorption and phase behavior are studied by the DFT method. Both nitrogen and methane molecules are modeled as Lennard-Jones spherical molecules, and the well-known Steele‘s 10-4-3 potential is used to represent the interaction between the fluid molecule and the solid wall. In order to test the combined method and the PSD model, the Intelligent Gravimetric Analyzer (IGA-003) was used to measure the adsorption of methane on the AMCMB. The DFT results are in good agreement with the experimental data. Based on these facts,we predict the adsorption amount of methane, which can reach 32.3ω at 299K and 4 MPa. The results indicate that the AMCMBs are a good candidate for adsorptive storage of methane and natural gas. In addition, the capillary condensation and hysteresis phenomenon of methane are also observed at 74.05K.     

Monte Carlo Simulation and Experimental Studies of CO2, CH4 and Their Mixture Capture in Porous Carbons

Adsorption of carbon dioxide and methane in porous activated carbon and carbon nanotube was studied experimentally and by Grand Canonical Monte Carlo (GCMC) simulation. A gravimetric analyzer was used to obtain the experimental data, while in the simulation we used graphitic slit pores of various pore size to model activated carbon and a bundle of graphitic cylinders arranged hexagonally to model carbon nanotube. Carbon dioxide was modeled as a 3-center-Lennard-Jones (LJ) molecule with three fixed partial charges, while methane was modeled as a single LJ molecule. We have shown that the behavior of adsorption for both activated carbon and carbon nanotube is sensitive to pore width and the crossing of isotherms is observed because of the molecular packing, which favors commensurate packing for some pore sizes. Using the adsorption data of pure methane or carbon dioxide on activated carbon, we derived its pore size distribution (PSD), which was found to be in good agreement with the PSD obtained from the analysis of nitrogen adsorption data at 77 K. This derived PSD was used to describe isotherms at other temperatures as well as isotherms of mixture of carbon dioxide and methane in activated carbon and carbon nanotube at 273 and 300 K. Good agreement between the computed and experimental isotherm data was observed, thus justifying the use of a simple adsorption model.     

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.     

Porous Texture and Surface Character of Dehydroxylated and Rehydroxylated MCM-41 Mesoporous Silicas-Analysis of Adsorption Isotherms of Nitrogen Gas and Water Vapor

Four samples of MCM-41 mesoporous silicas whose average pore diameters are 2.4, 2.8, 3.2, and 3.6 nm were prepared using sodium orthosilicate and cationic surfactants of [CH(3)(CH(2))(n)N(CH(3))(3)]X (n=11, 13, 15, 17). These four samples were calcined at 1123 K in vacuo to obtain the dehydroxylated samples, which were further rehydroxylated at 298 K to obtain the rehydroxylated samples. The adsorption isotherms of nitrogen gas (77 K) for the 12 MCM-41 mesoporous silicas are of Type IVc, giving no adsorption hysteresis. On the other hand, the first adsorption isotherms of water vapor (298 K) for the dehydroxylated MCM-41 samples are quite different from those of nitrogen gas, giving the remarkable adsorption hysteresis. The second water isotherms for the rehydroxylated MCM-41 samples are of Type IV, showing slight hysteresis. Using the nitrogen isotherms, the relation between the pore size and carbon chain length of the surfactant has been determined, and the effect of dehydroxylation and rehydroxylation on the porous texture has been examined. Using the first and second water isotherms, the adsorption model of physisorbed waters adsorbed on the surface silanol groups has been proposed. From the pore size distribution curves of nitrogen and water, the presence of constrictions in the cylindrical pores has been predicted. Copyright 2000 Academic Press.     

密度泛函与分子模拟计算介孔孔径分布比较

用巨正则系综Monte Carlo模拟(GCMC)方法和密度泛函理论（ DFT）结合统计积分方程（SIE）计算了介孔材料的孔径分布.为比较这两种方法,以77 K氮气在介孔活性碳微球中的吸附数据为依据,求出其孔径分布.在GCMC模拟和DFT计算中,流体分子模型化为单点的Lerrnard-Jones球;流体分子与吸附剂材料之间的作用采用平均场理论中的10-4-3模型.在DFT方法中,自由能采用Tarazona 提出的加权近似密度泛函方法(weighted density approximation,WDA)求解.结果表明,对于孔径大于1.125 nm的介孔材料,GCMC和DFT两种方法都可以用来研究介孔材料的孔径分布;对于小于1.125 nm的介孔材料,不能用DFT方法计算孔径分布（DFT方法本身的近似产生了误差）,只能用分子模拟方法.     

Rigid sphere molecular model enables an assessment of the pore curvature effect upon realistic evaluations of surface areas of mesoporous and microporous materials

A gas adsorption rigid spheres model (RSM) was incorporated into the CPSM model (corrugated pore structure model) to correlate the pore surface areas obtained from the BET and CPSM methods. The latter is a method simulating the gas sorption hysteresis loop and enables the evaluation of surface areas S(CPSM) through the integration of the pertinent pore size distributions. Thus, S(CPSM) values are inherently influenced by pore curvature. The new CPSM-RSM version estimates surface areas S(CPSMfs) that are independent of pore curvature and can be compared with the pertinent S(BET) values. The RSM exploits the fact that a curved pore surface accommodates fewer molecules, assumed to behave as rigid spheres, than an equal flat one. Thus, the RSM accounts for a higher molecular surface coverage Ac (nm2/molec.) in pores with marked curvature than that (i.e., Af) on a flat surface. The ratio Ac/Af for nitrogen adsorbed on single pore sizes varies in the range Ac/Af = 1.44-1.03 for pore sizes D = 1.5-15 nm, respectively. Also for D = 1.5-5.0 nm the S(CPSMfs) and S(BET) values are lower by approximately 10-45% than the S(CPSM) estimates. From the application of the CPSM-RSM model on several porous materials exhibiting all known types of sorption hysteresis loops, it was confirmed that S(BET) approximately S(CPSMfs) (+/-5%) and (S(CPSM) - S(BET))/S(BET) = 3-68% for the materials examined. In conclusion, the BET method may produce quite conservative surface area estimates for materials exhibiting pore structures with appreciable pore curvature, whereas the CPSM-RSM model can reliably predict both S(CPSM) and S(CPSMfs) = S(BET) values.     

交联聚苯乙烯型多孔吸附剂的中孔性质研究

采用77K温度下的氮气吸附方法,测定了经悬浮聚合制备的不同交联度的交联聚苯乙烯多孔吸附剂的吸附/脱附等温线.根据BET吸附模型计算了比表面,由吸附量计算了总的孔体积,由孔体积和比表面计算出平均孔径,并依据脱附等温线采用BJH方法计算孔径分布.结果表明,交联度对交联聚苯乙烯多孔吸附剂的孔结构均具有显著影响.随着交联聚苯乙烯多孔吸附剂的交联度升高,其孔径变小,比表面增大,而且低交联度吸附剂的中孔接近圆柱形,高交联吸附剂的中孔形状接近“墨水瓶”形.显然,交联度对孔性质的影响与孔结构在交联聚苯乙烯多孔吸附剂制备和后处理过程中的稳定性密切相关.交联度低时,初期形成的小孔不能保持稳定,在后续聚合及后处理过程中合并为大孔,结果造成低交联吸附剂大孔径、低比表面的现象.通过对孔径分布的研究,揭示了不同吸附剂在中孔范围内的孔特征,并对其形成机制进行了分析.     

Why the pore geometry model could affect the uniqueness of the PSD in AC characterization

In this paper we discuss why the pore geometry can affect the unicity of the pore size distribution (PSD) of a given activated carbon (AC) sample, when different probe gases are used in adsorption measures. In order to characterize the solid sample we used grand canonical Monte Carlo simulation and the independent pore model with slit or triangular pore geometry, focusing our analysis on the possibility of representing the adsorptive processes of a triangular pore of defined size by means of a combination of slit pores of different sizes. This representation is tested on experimental adsorption data of N₂ (77 K) on AC samples and acceptable results were obtained. Finally, we have performed a theoretical test, which consisted of analyzing a virtual porous solid with this approach and different probe gases (N₂ at 77 K and CO₂ at 273 K), showing that the differences between the pore representations can cause differences between the solid representations for the adsorptive properties, for these different gases. The analysis presented here can be extended to other pore geometries and other adsorbates, and provide arguments to further explain results presented in our previous paper, which refers to cases when different adsorbates yield different PSDs for a given sample and the same pore geometry model.     

Preparation and characteristics of electrospun activated carbon materials having meso- and macropores

Mesoporous activated carbon samples were prepared from electrospun PAN-based carbon fibers using physical activation with silica. Textural characterization was performed using nitrogen adsorption at 77 K. The BET specific surface area and pore size distribution of silica activated carbon materials were investigated. According to the increment of silica, BET specific surface area was increased about thirty times and it was found that silica activated carbon materials were highly mesoporous by studying pore surface distribution and pore volume distribution. Surface morphology of silica activated carbon materials were observed by SEM images. The spherical typed carbon materials were investigated. The diameter of spherical typed carbon materials was increased in proportional of the increment of silica.     

Preparation and characterization of double metal-silica sorbent for gas filtration

This paper presents the preparation of a porous (Mg, Ca) silicate structure, which could be employed as sorbent filter media. The sorbents have been prepared using sodium silicate precipitated with various ratios of magnesium and calcium salts. The sorbents obtained were characterized using scanning electron microscope (SEM), X-ray diffraction (XRD) and nitrogen physisorption isotherm. Further, the applicability and performance of the sorbent impregnate with potassium hydroxide for removal of sulphur dioxide (SO₂) has been demonstrated. From the isotherms, specific surface area, pore diameter and volume of pores were estimated. Results show that the chemical composition and textural properties of the resultant sorbents were highly dependent on Mg/Ca molar ratio. It was found that sorbents made with 68 mol% Mg and 32 mol% Ca (PSS-MgCa-68/32); and 75 mol% Mg and 25 mol% Ca (PSS-MgCa-75/25) exhibited even higher specific surface area and pore volume than the sorbents containing a single metal. The Mg/Ca-silica sorbents obtained contains interconnected bimodal porosity with large portions being mesopores of varied sizes. The pore size distribution (PSD) results further indicate that PSS-MgCa-68/32 sorbent exhibits wide PSD of interconnected pores in the size range of 1 to 32 nm while PSS-MgCa-50/50 and PSS-MgCa-75/25 exhibits narrow PSD of 1 to 5 nm. Using SO₂ as model contaminate gas, it was shown that the dynamic adsorption performance of the PSS-MgCa-sorbents impregnated with 8 wt% KOH exhibits SO₂ uptake, with impregnated PSS-MgCa-68/32 showing better performance. This shows that the materials prepared can be used as adsorbent for gas filtration.     

Immersion Calorimetry: Molecular Packing Effects in Micropores

Repeated and controlled immersion calorimetry experiments were performed to determine the specific surface area and pore‐size distribution (PSD) of a well‐characterized, microporous poly(furfuryl alcohol)‐based activated carbon. The PSD derived from nitrogen gas adsorption indicated a narrow distribution centered at 0.57±0.05 nm. Immersion into liquids of increasing molecular sizes ranging from 0.33 nm (dichloromethane) to 0.70 nm (α‐pinene) showed a decreasing enthalpy of immersion at a critical probe size (0.43–0.48 nm), followed by an increase at 0.48–0.56 nm, and a second decrease at 0.56–0.60 nm. This maximum has not been reported previously. After consideration of possible reasons for this new observation, it is concluded that the effect arises from molecular packing inside the micropores, interpreted in terms of 2D packing. The immersion enthalpy PSD was consistent with that from quenched solid density functional theory (QSDFT) analysis of the nitrogen adsorption isotherm.     

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.     

Correct procedures for the calculation of heats of adsorption for heterogeneous adsorbents from molecular simulation

Several procedures for calculating the heat of adsorption from Monte Carlo simulations for a heterogeneous adsorbent are presented. Simulations have been performed to generate isotherms for nitrogen at 77 K and methane at 273.15 K in graphitic slit pores of various widths. The procedures were then applied to calculate the heat of adsorption of an activated carbon with an arbitrary pore size distribution. The consistency of the different procedures shows them to be correct in calculating interaction energy contributions to the heat of adsorption. The currently favored procedure for this type of calculation, from the literature, is shown to be incorrect and in serious error when calculating the heat of adsorption of activated carbon.     

Pore accessibility of N2 and Ar in disordered nanoporous solids: theory and experiment

Recently (Nguyen and Bhatia, J. Phys. Chem. C 111:2212–2222, 2007) we have proposed a new algorithm utilising cluster analysis principles to determine pore network accessibility of a disordered material. The algorithm was applied to determine pore accessibility of the reconstructed molecular structure of a saccharose char, obtained in our recent work using hybrid reverse Monte Carlo simulation (Nguyen et al., Mol. Simul. 32:567–577, 2006). The method also identifies kinetically closed pores not accessed by adsorbate molecules at low temperature, when their low kinetic energy cannot overcome the potential barrier at the mouths of pores that can otherwise accommodate them. In the current work, the results are validated by transition state theory calculations for N₂ and Ar adsorption, showing that N₂ can equilibrate in narrow micropores at practical time scales at 300 K, but not at 77 K. Large differences between time scales for micropore entry and exit are predicted at low temperature for N₂, the latter being smaller by over three orders of magnitude. For N₂ at 77 K the time constant for pore entry exceeds 3 hr., while for exit it is 134 days. At 300 K these values are smaller than 1 μs, indicating good accessibility at this temperature. These results are verified by molecular dynamics simulations, which reveal that while N₂ molecules enter and leave all pores frequently at 300 K, entry and exit events for apparently inaccessible pores are absent at 77 K. For Ar at 87 K better accessibility is evident for the saccharose char compared to N₂ at 77 K. This finding is now experimentally shown in this work by comparison of pore size distributions obtained from experimental nitrogen adsorption isotherms of nitrogen and argon at 77 K and 87 K.     

微孔椰壳焦孔结构表征

为了更深入地了解微孔生物质焦的孔隙结构特征,在水蒸气气氛下制备椰壳焦（CSCs）,并且采用了不同分子探针、计算模型和校准步骤对其进行表征。结果表明,椰壳焦有较高的碳含量和比较丰富的孔隙度,适合进一步活化以制备活性炭。表征椰壳焦较为合适的方法是：以Ar为分子探针,并采用非定域密度泛函（NLDFT）模型。当校准步骤优先进行时,以N₂和Ar为分子探针的吸附测试结果如孔径分布（PSD）和吸附等温线会受到孔隙阻塞的影响,从而错误地描述椰壳焦的孔隙结构。实验结果还表明,273 K下仪器的真空处理可以去除绝大部分残留的He,降低孔隙阻塞的影响。     

改性Y沸石的孔结构与催化性能

测定了不同方法改性的Y沸石样品的N_2吸附和脱附等温线, 并计算了样品的微孔、大孔和二次孔的孔容和表面积, 以及样品的二次孔分布, 证实改性方法对样品的孔结构有显著的影响。同时, 还考察了不同尺码探针分子在改性Y沸石样品上的酸催化反应活性, 将所得数据与样品的酸量、酸强度和二次孔容相关联, 取得了满意的结果。说明对大尺码反应分子, 改性过程中生成的大孔径二次孔, 对提高沸石催化剂的反应活性是有利的。     

Preparation and structural characterization of activated carbons based on polymeric resin

In this work, activated carbons (ACs) with high porosity were synthesized from polystyrene-based cation-exchangeable resin (PSI) by chemical activation with KOH as the activating agent. And the influence of the KOH-to-PSI ratio on the porosity of the ACs studied was investigated by using nitrogen adsorption isotherms at 77 K and a scanning electron microscope (SEM). As a result, PSI could be successfully converted into ACs with well-developed micro- and mesopores. The specific surface area and pore volumes increased with an increase in the KOH-to-PSI ratio. However, it was found that the addition of KOH did lead to the transformation of the micropores to the meso- and macropores. From the results of pore size analysis, quite different pore size distributions were observed, resulting from the formation of new pores and the widening of the existing micropores during KOH activation. A SEM study showed that the resulting carbons possessed a well-developed pore structure and the pore size of the ACs studied increased with the KOH-to-PSI ratio.     

Surface analysis of cryofixation-vacuum-freeze-dried polyaluminum chloride-humic acid (PACl-HA) flocs

The powder of polyaluminum chloride-humic acid (PACl-HA) flocs was prepared by cryofixation-vacuum-freeze-drying method. The FTIR spectra show that some characteristic functional groups in polyaluminum chloride (PACl), humic acid (HA), and kaolin still existed in the dried flocs. X-ray diffractometry (XRD) patterns indicate that these flocs are amorphous. Nitrogen adsorption-desorption isotherms were obtained for different samples of the dried PACl-HA flocs. The BET specific surface area, BJH cumulative absorbed volume and BJH desorption average pore diameter of them were determined. The peak values of 8.4-11.2 nm (pore diameter) for pore size distribution (PSD) curves indicate that the pores of the dried flocs are mostly mesopores. The surface fractal dimensions D(s) and the corresponding fractal scales determined from both SEM images and nitrogen adsorption-desorption data sets reveal the multi-scale surface fractal properties of the dried PACl-HA flocs, which exhibited two distinct fractal regimes: a regime of low fractal dimensions (2.07-2.26) at higher scales (23-387 nm), mainly belonging to exterior surface scales, and a higher fractal dimensions (2.24-2.37) at lower scales (0.80-7.81 nm), falling in pore surface scales. Both HA addition and kaolin reduction in dried floc can decrease the irregularity and roughness of external surface. However, for the irregularity and roughness of pore surface, the addition of HA or kaolin in dried floc can increase them. Furthermore, some difference was found between the pore surface fractal dimensions D(s) calculated from nitrogen adsorption and desorption data. The pore surface D(s) values calculated through thermodynamic model were much greater than three.