Using DFT analysis of adsorption data of multiple gases including H2 for the comprehensive characterization of microporous carbons

Hydrogen and nitrogen adsorption isotherms at cryogenic temperatures (77 and 87 K) were used to characterize the microporosity of a series of activated carbons, representing various pore size distributions (PSD). The PSD for each carbon was calculated by simultaneous fitting of the DFT model isotherms to their experimental counterparts. The resulting PSD represents robust characteristics of the carbon structure that is consistent with all the data used in the analysis. The range of pore size analysis in this method is extended to smaller pore sizes compared to the standard nitrogen adsorption analysis. In addition, it is shown that this approach allows to detect and exclude experimental points that are not fully equilibrated due to diffusion problems in narrow micropores. The results of the analysis of a series of carbons activated with systematically increasing burn-off show that the presented approach is a useful tool for a comprehensive characterization of microporous carbons, and for obtaining detailed and reliable carbon PSDs.     

Adsorption characteristics of bamboo activated carbon

Dye is difficult to remove from aqueous solution with common adsorbents due to its large molecular size. Mesoporous bamboo activated carbon is utilized in the adsorption of Black 5, Red E and phenol. The adsorption performance of the carbon is experimentally examined along with the characterization of the adsorbent. The comparison of adsorption capacity of the bamboo activated carbon with that of coconut activated carbon and carbon cryogel indicates that the large volume of mesopore in the carbon helps the expansion of adsorption capacity. Microscopic observation, the measurement of pore characteristics and fitting to the adsorption isotherms are conducted in the characterization of the bamboo activated carbon.     

Synthesis,gas adsorption and reliable pore size estimation of zeolitic imidazolate framework-7 using CO2 and water adsorption

Reliable estimation of the pore size distribution(PSD) in porous materials such as metal–organic frameworks(MOFs) and zeolitic imidazolate frameworks(ZIFs) is crucial for accurately assessing adsorption capacity and corresponding selectivity. In this study, the so-called zeolitic imidazolate framework-7(ZIF-7) is successfully synthesized via relatively fast and convenient microwave technique. The morphology and structure of the obtained MOF were characterized by XRD, SEM and N_2 and CO_2adsorption/desorption isotherms at 77 K and0 °C respectively. Then, to determine the PSD of the fabricated MOF, carbon dioxide isotherms are experimentally measured at various temperatures up to atmospheric pressure. Afterward, the experimental CO_2 isotherms data are utilized in two recently proposed in-house algorithms of SHN1 and SHN2 to extract the true PSD of manufactured ZIF-7. The obtained results revealed that median pore diameter of the fabricated ZIF-7 is estimated around 0.404 nm and 0.370 nm by using CO_2 isotherms at 273 K and 298 K respectively. These values are in good agreement with the real pore diameter of 0.42 nm. Moreover, experimental data of water adsorption isotherms over four different MOFs, borrowed from literature, are employed to illustrate further effectiveness of the above algorithms on successful determination of the corresponding pore size distributions. All predicted PSDs are proved to be in good agreement with those obtained from independent methods such as topology and morphology studies.     

用近似Broekhoff方程计算孔径分布

本文对计算孔径分布的Broekhoff方程做了简化,得到一组近似方程,实例计算结果证明它和原方程等效.近似方程的优点在于能制成专用机与吸附仪联用,加快数据处理.近似方程的适用范围为:10(?)—300(?)     

Evaluation of Adsorption Properties of Low Surface Area Carbons—Comparison of Experiments with a Theoretical Study

Adsorption isotherms of nitrogen, argon and methane were experimentally measured at 77 K on low surface area graphitised carbons and natural graphite. For direct comparison, theoretical isotherms for the same gases were calculated on a model, flat surface by using NL DFT. Vulcan (a graphitised carbon black, often used as a surface area standard) was shown to represent a good approximation of a flat graphite surface. It is a suitable material for evaluation of potential parameters in modelling of adsorption in micropores. It was also confirmed that the non-local density functional theory provided a good and reliable fit to experimental adsorption isotherms. SEM microscopy and x-ray diffraction revealed surface properties consistent with those evaluated by adsorption.     

The significance of physical factors on the adsorption of polyaromatic compounds by activated carbons

The adsorption of three synthetic organic compounds (SOCs) (i.e., phenanthrene, biphenyl, and 2-chlorobiphenyl), with similar physicochemical properties but different molecular conformations (i.e., planar and nonplanar), by an activated carbon and an activated carbon fiber was investigated. The physical characteristics of the carbons were obtained from low temperature nitrogen adsorption isotherms using BET, DR, and DFT models. Their surface chemistry was characterized by water vapor adsorption, pH of the point of zero charge, acid/base uptakes, and elemental analysis. The results indicated that adsorbent pore structure characteristics and adsorbate molecular conformation are important in the adsorption of SOCs by porous carbonaceous adsorbents. To predict the adsorption of SOCs by activated carbons, accurate characterization of pore shape and size distribution in primary micropores is important. The results indicated that adsorbate molecules can access and fill more efficiently the slit-shape pores than ellipsoidal pores, whereas the ellipsoidal pores create higher adsorption potential than slit-shape pores. Both molecular conformation and dimensions of adsorbate affect the adsorption. Planar molecules appear to access and pack in slit-shape pores more efficiently as compared to nonplanar molecules. Nonplanar molecular conformation weakens the interactions between adsorbate molecules and carbon surfaces.     

Surface area and pore structure of talc-magnesite

The effect of thermal treatment on talc-magnesite in the presence of air in the temperature range 500–1000°, was studied by nitrogen adsorption and followed by t.g.a., d.t.a. and X-ray analysis. From the nitrogen adsorption isotherms, the specific surface area as well as pore-size distribution was estimated. The surface area increased with temperature, to reach a maximum at 600°. On immersion of the calcination products in water, magnesium hydroxide was formed. Decomposition of the hydration products in air at 450° resulted in solids of relatively higher surface areas, whereas decomposition in vacuo at the same temperature produced more active solids. Surface area of the products produced in vacuo decreased only slightly with the primary decomposition temperature, and they are characterised by sharp pore-size distribution curves. Surface areas of the products produced in air were dependent on the primary calcination temperature, although they showed pore-size spectra similar to those of the other products. Products obtained by direct decomposition in air showed wider pore spectra that shifted towards higher pore radii with rise of temperature.     

Effect of Heating on Adsorption Behavior of Porous Glass

The effect of heat treatment and fluoridation of the surface on the adsorption of n -butane on porous glass was studied. The BET surface area, pore-size distribution, and porosity were obtained from N₂ isotherms of samples successively heated at temperatures from 350° to 865°C. Deformation of the bulk structure began at 700°C. A cylindrical pore model inadequately correlated changes in specific surface, mean pore radius, and porosity. Surface heterogeneity was decreased to some extent by heat treatment at 865°C. Treatment of the surface with HF caused no significant change in the heat of adsorption from that of the untreated sample. Adsorption sites other than surface silanol groups are proposed to explain the results.     

Quenched solid density functional theory method for characterization of mesoporous carbons by nitrogen adsorption

Quenched solid density functional theory (QSDFT) model for characterization of mesoporous carbons using nitrogen adsorption is extended to cylindrical and spherical pore geometries. The kernels of theoretical isotherms in the range from 0.4 to 50 nm are constructed accounting for different possible variations of the pore shapes in micropore and mesopore regions. The results of QSDFT method are illustrated with experimental data on adsorption on novel CMK-3 and 3DOm carbons. The proposed method is recommended for pore size distribution calculations for micro–mesoporous carbons obtained through various templating mechanisms.     

不同结构活性炭对CO_2、CH_4、N_2及O_2的吸附分离性能

制备了比表面积为1943 m2/g的纯微孔活性炭AC-1和比表面积为1567 m2/g,中孔比例为47.18%的活性炭AC-2.分别以AC-1及AC-2为吸附剂测定CO2、CH4、N2和O2的298 K吸附等温线,考察了两种活性炭对CO2/N2、CO2/CH4及CH4/N2气体混合物的吸附分离性能.实验结果表明,孔结构是影响吸附剂吸附分离性能的主要因素.富中孔活性炭AC-2较AC-1更适用于CO2/N2、CO2/CH4气体混和物的吸附分离,而微孔活性炭AC-1对CH4/N2混合体系的吸附分离性能优于AC-2.     

A multi-scale approach to the physical adsorption in slit pores

Adsorption isotherms are the foundation of gas storage and separation operations. The isotherm models are classified into three scale levels with empiricisms in macroscopic level, requirements of long computing time and idealized conditions in microscopic level, as well as gaps in knowledge between these two levels. A multi-scale modeling methodology is developed in this paper in order to reduce the identified limitations. Microscopic molecular simulations (MS) based on the grand canonical Monte Carlo (GCMC) method are carried out followed by the development of the localized adsorption isotherms defined as the intermediate level models. They are represented by the Boltzmann factor and the local Langmuir equations. The macroscopic models are then formulated through the integration of small scale models. The following three contributions are achieved in the paper. First of all, guidelines for the validity of the Boltzmann factor are established, showing its practical significance, and the local Langmuir isotherm is justified as a good approximation to the results from microscopic simulations. Secondly, it is demonstrated that the pore size distributions can be determined using GCMC simulations coupled with the measured adsorption isotherms as exemplified by a case study on a coal specimen. Finally, using the measurement data reported by Bae and Bhatia (2006) for carbon dioxide adsorption on coal, we show that the overall adsorption isotherms can be determined from the multi-scale approach through the integration of smaller scale models with pore size distributions without the empiricism, indicating the success of the methodology. Further work is needed to improve the prediction accuracy for methane adsorption on coal specimens.     

离子液体聚合物CO_2吸附性能研究

为提高离子液体吸附CO_2的性能,通过自由基聚合制备了季铵盐类离子液体聚合物,采用两步种子溶胀法使该聚合物形成多孔结构,并通过扫描电子显微镜和差热-热重分析法对其形貌和热稳定性进行表征。研究了4种溶胀剂制备的多孔聚合物吸附CO_2的性能,试验结果表明:制备的多孔聚合物具有发达的微孔结构,孔径在0.4~0.8 nm内连续分布,且较集中于0.5~0.6 nm,达到38%以上;溶胀剂的种类对孔径分布及累计孔容有显著的影响,可归因于溶胀剂与聚合物的溶解度差异,采用混合溶胀剂得到的孔径分布更加均匀,而采用环乙烷溶胀剂得到的累计孔容明显减少;多孔聚合物的CO_2吸附量主要受累计孔容的影响,累计孔容相当的聚合物吸附CO_2的量也近似,在273 K、0.101 MPa条件下,约为1.1%。     

甲烷在单壁碳纳米管中的吸附的密度泛函研究

纳米微孔材料的出现使得有可能在中低压下微孔介质中吸附存储天然气 .由于天然气的主要成分是甲烷 ,其吸附存储为研究者所关注 .碳纳米管由单层或几层纯碳同轴圆柱状结构层组成 ,每个管状层由碳六边形构成 ,与石墨内结构相似 .单壁的碳纳米管称为单壁碳纳米管 (ＳｉｎｇｌｅＷａｌｌｅｄＣａｒｂｏｎＮａｎｏｔｕｂｅ ,ＳＷＮＴ) .它作为一种吸附材料在实验和理论研究中受到高度重视 .在ＳＷＮＴ中吸附的密度泛函理论 (ＤＦＴ)研究与计算机模拟相比较少 .文献中只有Ｇｏｒｄｏｎ等[1] 在 1999年采用密度泛函的方法和过分简化的氢分子势能函…     

红霉素在大孔树脂上的吸附动力学研究

采用液膜及孔内扩散模型,模拟不同温度和不同红霉素(EM)初始浓度条件下,大孔吸附树脂HZ816及XAD16吸附红霉素的动态吸附曲线,并获得液膜传质及孔内扩散系数;考察了温度及溶质浓度对红霉素在两种树脂中吸附动力学的影响.结果表明,在实验范围内,红霉素在HZ816和XAD16两种树脂上的吸附平衡数据满足Langmuir吸附等温线方程,液膜及孔内扩散模型能较好地描述红霉素在两种树脂上的吸附动力学,同时,模型拟合得到的液膜传质系数随着温度的升高而增大,随着初始浓度的增大而增大,孔内扩散系数随着温度的升高而增大,随着初始浓度的增大而减小.     

Synthesis of Nanorods with Ni Cores and Porous Silica Coatings

Abstract  

Nanorods with a Ni core and a silica coating have been prepared using a one-step synthesis and characterized using a variety of methods. Nitrogen adsorption isotherms have been used to characterize the pore size and the internal surface area of the silica shells grown on the Ni nanorods. Spectroscopic characterization of CO adsorbed on the Ni nanoparticle cores has been used to verify that the pore structure of the silica shells allows CO to access the Ni core; this property is critical to the use of core–shell structures as industrial catalysts. To demonstrate their resistance to physical and chemical degradation, the properties of the silica-coated Ni nanoparticles have been measured both before and after treatment at high temperature (623 - 1073 K) and exposure to a reducing atmosphere (hydrogen gas). Annealing at high temperatures reduces, but does not eliminate, the porosity of the silica shells.     

Mathematical Modeling of the Dependence of the Vapor Permeability Coefficient of a Membrane on Its Pore Structure

The dependence of the vapor permeability coefficient of a distillation membrane on its pore structure is analyzed. The pore structure of the membrane is represented as a two- or three-dimensional network of capillaries that have a fixed length and originate at nodes with a constant coordination number. Three pore-size distribution functions are considered, namely, a uniform, a bimodal, and a triangular function. An explicit expression for the vapor permeability coefficient of the membrane is derived using orientation averaging and the smooth-field approximation. The effect of some structural properties (pore-size distribution, porosity, coordination number of a node, etc.) of the porous membrane on the vapor permeability coefficient is studied numerically. Irrespective of the pore-size distribution function, the vapor permeability coefficient decreases with increasing pore radius and grows with increasing coordination number and Knudsen number.     

Comparisons of pore properties and adsorption performance of KOH-activated and steam-activated carbons

Carbonaceous adsorbents with controllable pore sizes derived from carbonized pistachio shells (i.e., char) were prepared by the KOH activation and steam activation methods in this work. The pore properties including the BET surface area, pore volume, pore size distribution, and pore diameter of these activated carbons were characterized by the t-plot method based on N₂ adsorption isotherms. Through varying the KOH/char ratios from 0.5 to 3, the KOH-activated carbons exhibited BET surface areas ranging from 731 to 1687 m²/g with a similar micropore content (80–92%). The carbons activated by steam at 830 °C for 2 h had a BET surface area of 821 m²/g with the micropore content of 42%. The micropore/total pore volume ratio (V_micro/V_pore) and average pore size (D_pore) were independent of the KOH/char ratio, revealing that KOH activation is a powerful method in developing and controlling the number of micropores with a very similar pore size distribution. The adsorption equilibria and kinetics of methylene blue, basic brown 1, acid blue 74, 2,4-dichlorophenol, 4-chlorophenol, and phenol from water on all activated carbons at 30 °C were investigated to demonstrate the fact that adsorption of organics is not only dependent upon the BET surface area but is also determined by the relative size between pores and molecules. The adsorption isotherms were subjected to the model fitting according to Langmuir and Freudlich equations. By comparing the projected area of adsorbates, the surface coverage of phenols is about 3.6 times of that of dyes (based on unit gram of activated carbon). The Elovich equation was found to suitably describe the adsorption process of all KOH-activated carbons while the adsorption behavior on the steam-activated carbon was reasonably fitted with the intraparticle diffusion model.     

The effect of impregnation of activated carbon with SnCl2.2H2O on its porosity, surface composition and CO gas adsorption

Activated carbon was impregnated with different concentrations of SnCl₂.2H₂O. Unimpregnated and impregnated activated carbons were analysed by means of physical adsorption and XPS and were tested for CO gas adsorption in a PSA system. The adsorption isotherms of N₂ at 77 K were measured and showed a Type I isotherm indicating microporous carbon for all the samples. The surface area, pore volume and pore size distribution were reduced with impregnation. XPS analysis showed an increase in the intensity of Sn3d peak with impregnation. The impregnated activated carbon showed a very good adsorption ability of CO gas compared to the unimpregnated sample. The adsorptive species responsible for CO gas adsorption was confirmed to be SnO₂ instead of SnO due to the former’s comparative thermodynamic stability.     

Adsorption of Binary Gas Mixtures on Strongly Heterogeneous Surfaces

The integral equation (IE) approach coupled with a rectangular adsorption energy distribution and Mean Field Approximation (MFA) is used to describe the adsorption of single gases and their binary mixture on a heterogeneous solid surface. In particular, it is important to stress that all theoretical expressions shown are the exact solution of IE approach. During the analysis of single-gas adsorption isotherms also accompanying calorimetric effects are investigated. The problem of correlations between the best-fit parameters describing energetic heterogeneity and energy of intermolecular interactions is discussed. The predictions of the theory are compared with the experimental literature data. It is shown that the new theoretical adsorption isotherms give the results that are very close to the experimental data.