Modeling water adsorption in carbon micropores: study of water in carbon molecular sieves

Measurements of water adsorption equilibrium in a carbon molecular sieve are undertaken in order to gain insight into the nature of water adsorption in carbon micropores. The measurements are taken at low concentrations to emphasize the role of oxygen-containing functional groups in the adsorption of water. Comparisons are made with previously published water adsorption data at higher concentrations to provide a data set spanning a wide range of loading. The assembled data set provides an opportunity for comparison of various theories for prediction of water adsorption in carbon micropores. Shortcomings of current theories are outlined, and an analytical theory that is free of these deficiencies is proposed in this investigation. With the consideration of micropore volume and pore size distribution, the experimental data and proposed isotherm model are consistent with previous studies of Takeda carbon molecular sieves. Also investigated is the uptake kinetics of water, which is characterized by a Fickian diffusion mechanism. The Maxwell-Stefan formulation is applied to characterize the dependence of the diffusional mobility upon loading.     

An experimental and molecular simulation study of the adsorption of carbon dioxide and methane in nanoporous carbons in the presence of water

The adsorption of carbon dioxide and methane in nanoporous carbons in the presence of water is studied using experiments and molecular simulations. For all amounts of adsorbed water molecules, the adsorption isotherms for carbon dioxide and methane resemble those obtained for pure fluids. The pore filling mechanism does not seem to be affected by the presence of the water molecules. Moreover, the pressure at which the maximum adsorbed amount of methane or carbon dioxide is reached is nearly insensitive to the loading of preadsorbed water molecules. In contrast, the adsorbed amount of methane or carbon dioxide decreases linearly with the number of guest water molecules. Typical molecular configurations obtained using molecular simulation indicate that the water molecules form isolated clusters within the host porous carbon due to the nonfavorable interaction between carbon dioxide or methane and water.     

Modeling of adsorption on nongraphitized carbon surface: GCMC simulation studies and comparison with experimental data

We model nongraphitized carbon black surfaces and investigate adsorption of argon on these surfaces by using the grand canonical Monte Carlo simulation. In this model, the nongraphitized surface is modeled as a stack of graphene layers with some carbon atoms of the top graphene layer being randomly removed. The percentage of the surface carbon atoms being removed and the effective size of the defect (created by the removal) are the key parameters to characterize the nongraphitized surface. The patterns of adsorption isotherm and isosteric heat are particularly studied, as a function of these surface parameters as well as pressure and temperature. It is shown that the adsorption isotherm shows a steplike behavior on a perfect graphite surface and becomes smoother on nongraphitized surfaces. Regarding the isosteric heat versus loading, we observe for the case of graphitized thermal carbon black the increase of heat in the submonolayer coverage and then a sharp decline in the heat when the second layer is starting to form, beyond which it increases slightly. On the other hand, the isosteric heat versus loading for a highly nongraphitized surface shows a general decline with respect to loading, which is due to the energetic heterogeneity of the surface. It is only when the fluid-fluid interaction is greater than the surface energetic factor that we see a minimum-maximum in the isosteric heat versus loading. These simulation results of isosteric heat agree well with the experimental results of graphitization of Spheron 6 (Polley, M. H.; Schaeffer, W. D.; Smith, W. R. J. Phys. Chem. 1953, 57, 469; Beebe, R. A.; Young, D. M. J. Phys. Chem. 1954, 58, 93). Adsorption isotherms and isosteric heat in pores whose walls have defects are also studied from the simulation, and the pattern of isotherm and isosteric heat could be used to identify the fingerprint of the surface.     

Equilibrium and kinetics of water adsorption in carbon molecular sieve: theory and experiment

Measurements of water adsorption equilibrium and kinetics in Takeda carbon molecular sieve (CMS) were undertaken in an effort to characterize fundamental mechanisms of adsorption and transport. Adsorption equilibrium revealed a type III isotherm that was characterized by cooperative multimolecular sorption theory. Water adsorption was found to be reversible and did not display hysteresis upon desorption over the conditions studied. Adsorption kinetics measurements revealed that a Fickian diffusion mechanism governed the uptake of water and that the rate of adsorption decreased with increasing relative pressure. Previous investigations have attributed the observed decreasing trend in the rate of adsorption to blocking of micropores. Here, it is proposed that the decrease is attributed to the thermodynamic correction to Fick's law which is formulated on the basis of the chemical potential as the driving force for transport. The thermodynamically corrected formulation accounted for observations of transport of water and other molecules in CMS.     

Determination of the average heat and characteristic energy from the adsorption isotherm

The isotherms of the total content, isosteric and average heats of adsorption, as well as characteristic energies of adsorption were determined from the isotherms of excess adsorption of carbon dioxide on six different carbon adsorbents at temperature ranging from 293 to 423 К at pressures up to 6 MPa. The average isosteric heats are in agreement with the average heats of adsorption, which were determined from the equation relating the heat of adsorption with the characteristic energy of adsorption.     

甲烷在层状石墨烯和活性炭上的吸附平衡

以吸附式天然气（ANG）吸附剂的工程应用为目的,以0-10 MPa、283.15-303.15 K甲烷在层状石墨烯（GS（3D）,比表面积2062 m²/g）和活性炭SAC-01（比表面积1507 m²/g）上的吸附平衡数据作分析。首先,在77.15 K下由氮气吸附表征样品的孔径大小及分布（PSD）和比表面积。其次,选择极低压力下的吸附平衡数据标定亨利定律常数,确定甲烷在两吸附剂上的极限吸附热,并由维里方程和10-4-3势能函数计算甲烷与两吸附剂壁面之间的相互作用势。最后,依据测试的甲烷在吸附剂上的高压吸附平衡数据,比较了Langmuir系列方程的关联数据后的拟合精度,并由绝对吸附量计算了甲烷的等量吸附热。结果表明,甲烷在GS（3D）和活性炭SAC-01上的平均极限吸附热为23.07、20.67 kJ/mol;283.15 K下甲烷分子与GS（3D）和活性炭SAC-01之间的交互作用势ε_sf/k为67.19、64.23 K,与洛伦混合法则的计算值64.60 K相近;Toth方程关联甲烷在活性炭SAC-01和GS（3D）上吸附平衡数据的拟合累计相对误差为0.25%和2.29%;甲烷在活性炭SAC-01和GS（3D）上的等量吸附热平均值为16.8和18.3 kJ/mol。相对于活性炭SAC-01,比表面积和微孔容积均较高的GS（3D）对甲烷的吸附更具有优势。     

Adsorption of butane isomers and SF6 on Kureha activated carbon: 1. Equilibrium

Adsorption equilibria of butane isomers and SF6 on Kureha activated carbon were investigated using the volumetric method and the tapered element oscillating microbalance (TEOM) technique. The isotherm data of the butane isomers measured by the TEOM technique are in good agreement with those determined by the volumetric method. Single-component adsorption isotherms are reported at temperatures in the range from 298 to 393 K and at pressures up to 120 kPa. SF6 molecules are mainly adsorbed in the larger micropores, resulting in a lower adsorption capacity. The amount adsorbed for n-butane is slightly higher than that for isobutane in the whole range investigated. This is attributed to the fact that the linear n-butane molecule can adsorb in the smaller micropores. The T6th model appropriately describes the equilibrium data of the butane isomers, while the isotherm data of SF6 can be fitted by the Langmuir model. The isosteric heats associated with adsorption for these three adsorptives show different loading dependences. The present study indicates that the activated carbon can be well characterized by the probe molecules having different molecular sizes.     

甲烷在石墨化热解碳黑和活性炭上的吸附

为研究影响碳基吸附剂吸附超临界温度气体的主要因素,选择石墨化热解碳黑BP280和Ajax活性炭,分析超临界温度高压甲烷在其上的吸附平衡。应用容积法,在压力0~20.5 MPa、温度253 K~313 K测定甲烷的吸附平衡数据,并由等量吸附线标绘和亨利定律常数确定等量吸附热。引入通用吸附等温方程,再由方程的Langmuir标绘确定最大吸附容量,进而通过方程的线性化计算吸附平衡态中甲烷分子的作用能。结果表明,甲烷在两种吸附剂上的最大吸附容量均随温度而变化,并都小于液态甲烷的密度;甲烷在碳黑和活性炭上的等量吸附热分别为11.9 kJ/mol~12.5 kJ/mol和17.5 kJ/mol~22.5 kJ/mol,体现了两种吸附剂不同的表面能量分布;甲烷分子间作用能随吸附量的变化特点反映了超临界温度甲烷以类似于压缩气体状态聚集的特点和吸附剂结构上的差异。碳基吸附剂的比表面积和微孔容积是影响其储存甲烷容量的重要因素。     

On the anatomy of the adsorption heat versus loading as a function of temperature and adsorbate for a graphitic surface

In this paper we review and classify the various patterns of isosteric heat versus loading for adsorption of gases on graphitised thermal carbon black at temperatures ranging from below the 3D triple point to temperatures above it, but less than the 3D critical point. We have identified the features of heat curve and highlighted the microscopic origin of these features. The patterns vary with temperature and with the relative strength of the fluid-fluid interaction and solid-fluid interaction. For simple adsorptives (by simple we meant there is no strong association between fluid particles), the heat curve is typified by fluid-fluid attraction and layering phenomena. For adsorptives showing strong association such as water, ammonia and methanol, the heat curve essentially begins below the condensation heat and then approaches it as loading is increased. This is mainly due to the strong hydrogen bonding in these fluids. A third group includes adsorptives such as benzene, where the heat curve is constant in the sub-monolayer coverage region (but is higher than the condensation heat) and then drops off to the condensation heat when higher layers are formed. The constant heat in the sub-monolayer region is due to the balance between the energy factor (from fluid-fluid interaction) and entropy factor (due to re-orientation of adsorbed molecules). Our proposed classification is supported by detailed GCMC simulations of various gases that have been reported in the literature, and we supplement these with new results for the adsorption of xenon on graphite to investigate in more detail the change in heat pattern with temperature. Xenon is chosen because of its high fluid-fluid interaction, allowing us to study the 2D-phase transition in the first as well as higher layers.     

Effect of water and alkali modifications on ETS-10 for the cycloaddition of CO2 to propylene oxide

Sodium oxide (NaOx) impregnated Engelhard Titanosilicate-10 (ETS-10) molecular sieve catalysts were prepared to enhance the basicity associated with ETS-10 and subsequently investigated for the cycloaddition of carbon dioxide to propylene oxide to produce propylene carbonate. For dry NaOx-modified ETS-10 catalysts that contained no adsorbed water, a maximum yield of propylene carbonate was achieved at a loading of 2.0 excess NaOx species per unit cell. However, the greatest enhancements in the rate of reaction were observed when small amounts of water were adsorbed onto the unmodified ETS-10 catalyst immediately prior to reaction. Surface-bound water appears to enhance the surface Bronsted acidity of the unmodified ETS-10 catalyst via the formation of surface -OH groups at lower water loadings, producing a surface of better-tuned acid-base bifunctional characteristics for the cycloaddition reaction. At levels of hydration greater than 12.5% by mass, the yield of propylene carbonate was further enhanced, but at a smaller rate than that observed at lower rehydration levels, which is more indicative of an enhanced transport effect. Adsorption microcalorimetry of carbon dioxide indicated that, at loadings less than 2.0 NaOx per unit cell, the total uptake of the CO2 adsorption sites required for the reaction were less than in the parent ETS-10 material. However, at higher levels of NaOx occlusion, where the total uptake and strength of the adsorption sites exceeded those observed for the as-received ETS-10 material, the cycloaddition activity of this catalyst suffered due to the reduced pore volume and surface area. It appears that precise tuning of both the surface acidity and basicity is crucial in creating an effective acid-base bifunctional ETS-10 catalyst for the cycloaddition reaction investigated.     

Comparative features of ar adsorption on smooth and amorphous surfaces examined by density functional theory

We analyze argon adsorption isotherms and isosteric heat of adsorption on graphitized and nongraphitized carbon black and silica surfaces by means of nonlocal density functional theory (NLDFT). It is shown that in the case of graphitized carbon black the behavior of the adsorbed phase is nearly identical to that in the bulk phase at a distance larger than about 3-4 molecular diameters from the surface. At a smaller distance argon forms solid-like molecular layers at a temperature at least 3.5 K above the triple point, with the interlayer distance being markedly smaller than the argon collision diameter. In the case of defected or amorphous surfaces adsorbed argon is liquid-like below its triple point. Our extension of the Tarazona NLDFT to amorphous solids (NLDFT-AS) and the Kierlik and Rosinberg version of NLDFT excellently fit argon adsorption isotherms and properly predict the isosteric heat of adsorption. We showed that the surface roughness affects the calculated heat of adsorption, which allowed us to adjust the width of the diffuse zone of the nongraphitized carbon black and the silica surface.     

Accurate correlation,structural interpretation,and thermochemistry of equilibrium adsorption isotherms of carbon dioxide in zeolite NaX by means of the GSTA model

Zeolite NaX (commonly known as zeolite 13X) has found wide use in industry for the separation of carbon dioxide from air, methane-containing landfill gas, and flue gases. Capture and sequestration of carbon dioxide has become of utmost importance to mitigate severe environmental problems associated to burning of fossil fuels, such as the greenhouse effect and the consequential warming of global climate. Due to its low energy consumption and ease of operation, the zeolite-13X molecular-sieve pressure-swing adsorption process has become the method of choice for the recovery and capture of carbon dioxide from air and flue gas. Accurate correlation of the equilibrium adsorption isotherms of carbon dioxide in zeolite NaX is required for the reliable modeling and simulation of that process. In this paper, we firstly show that none of the traditional adsorption isotherm models (such as those of Langmuir, Sips, Toth, UNILAN, and Dubinin–Astakhov) is entirely capable of correlating a published set of equilibrium adsorption isotherms of carbon dioxide in zeolite NaX that were measured over a range of eight decades of pressure. A generalized statistical thermodynamic adsorption (GSTA) model, which we had already derived and successfully applied to the adsorption of water vapor in zeolite 3A, is employed in this work to obtain a very accurate correlation of that set of adsorption isotherms of carbon dioxide in zeolite NaX, for the pressure range from 0.2 Pa to 6.4 MPa and in the temperature range from −78 to 150 °C. We also provide thermochemical and structural interpretations of the isotherms fit and make predictions for the isosteric heat of adsorption that are in excellent agreement with the available experimental data.     

Adsorption of hexane, cyclohexane, and benzene on microporous carbon obtained by pyrolysis of hypercrosslinked polystyrene

The relationships of adsorption of hexane, cyclohexane, and benzene on a D4609 microporous carbon adsorbent obtained by the pyrolysis of hypercrosslinked polystyrene are compared. It is shown that in the range of relative pressures corresponding to the filling of ultramicropores, the adsorption behaviors of cyclohexane and benzene are essentially identical, in contrast to hexane, which is characterized by higher adsorption values and isosteric heat of adsorption. The observed relationships are explained by the steric features of the distribution of molecules of various structures in ultramicropores.     

Thermodynamics of methane adsorption on the microporous carbon adsorbent ACC

The behavior of the thermodynamic functions (differential molar isosteric heat of adsorption, entropy, enthalpy, and heat capacity) of the adsorption system methane—microporous carbon adsorbent ACC was analyzed at different adsorption equilibrium parameters in the temperature interval from 177.65 to 393 K and in the pressure range from 1 Pa to 6 MPa. The influence of the nonideal character of the gas phase and noninertness of the adsorbent were taken into account, which resulted in the appearance of the temperature dependence of the isosteric heat of adsorption, especially in the region of high pressures of the adsorptive. For the system studied, nonideality of the gas phase exerts the main effect on the thermodynamic functions of the adsorption system. In this interval of the parameters of the adsorption system, the correction to the noninertness of the adsorbent is not higher than 2.5%. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1765–1771, September, 2008.     

Adsorption of benzene on graphitized thermal carbon black: reduction of the quadrupole moment in the adsorbed phase

The performance of intermolecular potential models on the adsorption of benzene on graphitized thermal carbon black at various temperatures is investigated. Two models contain only dispersive sites, whereas the other two models account explicitly for the dispersive and electrostatic sites. Using numerous data in the literature on benzene adsorption on graphitized thermal carbon black at various temperatures, we have found that the effect of surface mediation on interaction between adsorbed benzene molecules must be accounted for to describe correctly the adsorption isotherm as well as the isosteric heat. Among the two models with partial charges tested, the WSKS model of Wick et al. that has only six dispersive sites and three discrete partial charges is better than the very expensive all-atom model of Jorgensen and Severance. Adsorbed benzene molecules on graphitized thermal carbon black have a complex orientation with respect to distance from the surface and also with respect to loading. At low loadings, they adopt the parallel configuration relative to the graphene surface, whereas at higher loadings (still less than monolayer coverage) some molecules adopt a slant orientation to maximize the fluid-fluid interaction. For loadings in the multilayer region, the orientation of molecules in the first layer is influenced by the presence of molecules in the second layer. The data that are used in this article come from the work of Isirikyan and Kiselev, Pierotti and Smallwood, Pierce and Ewing, Belyakova, Kiselev, and Kovaleva, and Carrott et al.     

AlPO4-11分子筛的吸附热力学性质

AlPO_4-n系列分子筛是八十年代初由美国联合碳化物公司开发的一类新型分子筛,据报导到目前为止已经合成出20种不同型号结构的AlPO_4分子筛。经X-射线多晶和单晶衍射结构分析,部分AlPO_4分子筛的结构已搞清楚,AlPO_4-11结构也已经测定,它具有十元环一维孔道,孔口大小为0.67nm×0.40nm的分子筛。     

Importance of molecular shape in the adsorption of nitrogen,carbon dioxide and methane on surfaces and in confined spaces

The importance of shape in the adsorption of nitrogen, carbon dioxide and methane (common molecular probes for solid characterization) on surfaces and in confined spaces is investigated for its effects on the adsorption capacity and isosteric heat. We study the possibility of using an equivalent pseudo-sphere model to describe the potential energy of interaction of these molecular probes. On a flat open surface, we find that the equivalent pseudo-sphere model describes adsorption of these species sufficiently well. However, in the confined space of pores, especially pores that accommodate three layers or less, the pseudo-sphere model describes the adsorption badly because of the geometrical constraint on the molecular packing. It is recommended that to study adsorption properly in small pores, potential models that correctly describe molecular shape should be used. In characterization, pseudo-sphere models are commonly used to generate the kernels (local isotherms) for the determination of pore size distribution which can lead to misleading results. We illustrate this with an example to show that the wrong pore size distribution results if pseudo-sphere kernels are used.     

超临界甲烷在活性炭上的吸附平衡分析

为分析由吸附平衡时的热力参数确定吸附量、吸附模型和等量吸附热精度的影响因素,选择在温度268.15~338.15 K和压力0~13.5 MPa测试的甲烷在Ajax活性炭上的吸附平衡数据,通过引入甲烷分子可进入活性炭吸附空间内的容积和可以不考虑甲烷在孔内吸附的临界孔宽的概念,依据甲烷在吸附平衡前后的总量守恒,确定甲烷在吸附池内的总量、绝对吸附量和过剩吸附量三者之间的关系式。结果表明,在引入吸附质分子可进入吸附空间内的容积和临界孔宽后,经由活性炭的孔径分布(PSD),可以准确计算甲烷在活性炭上的过剩吸附量;应用实验数据非线性回归Toth方程参数后,可由Gibbs关于吸附的定义确定甲烷在活性炭上的绝对吸附量。比较结果时发现,由于未考虑本体相中甲烷分子对吸附甲烷分子的影响,采用过剩吸附量的等量吸附线标绘确定的等量吸附热数值偏高,工程应用时应由绝对吸附量来确定等量吸附热。     

Isotope tracer study of hydrogen spillover on carbon-based adsorbents for hydrogen storage

A composite material comprising platinum nanoparticles supported on molecular sieve templated carbon was synthesized and found to adsorb 1.35 wt % hydrogen at 298 K and 100 atm. The isosteric heat of adsorption for the material at low coverage was approximately 14 kJ/mol, and it approached a value of 10.6 kJ/mol as coverage increased for pressures at and above 1 atm. The increase in capacity is attributed to spillover, which is observed with the use of isotopic tracer TPD. IRMOF-8 bridged to Pt/C, a material known to exhibit hydrogen spillover at room temperature, was also studied with the hydrogen-deuterium scrambling reaction for comparison. The isotherms were reversible. For desorption, sequential doses of H2 and D2 at room temperature and subsequent TPD yield product distributions that are strong indicators of the surface diffusion controlled reverse spillover process.