Nitrogen adsorption on fluorinated activated carbon fiber

Nitrogen adsorption isotherms for fluorinated activated carbon fiber (F-ACF) and fluorinated carbon black (F-CB) were measured at 77 K. Surface structures of F-ACF and F-CB were examined by _s -plot analysis using the adsorption data on the nonporous carbon black (CB) and F-CB. The surface energy of F-ACF was lower than that of ACF. The micropore structure of ACF was preserved even after fluorination, although the limiting adsorption amount and the micropore width decreased with fluorination.     

Calculation of henry constants for the adsorption of isomeric phenylenediamines on graphitized thermal carbon black

Henry constants for the adsorption of o- and p-phenylenediamines on the surface of graphitized thermal carbon black within the temperature range 433–479 K were calculated by the molecular statistical method. The parameters of the atom-atom potential function of intermolecular interaction between the nitrogen atom in aniline and isomeric phenylenediamines and the carbon atom of the basal face of graphite were determined. It was shown that an intramolecular H bond influenced the geometry and adsorption properties of o-phenylenediamine.     

The adsorptivity of organic substances with various physico-chemical properties

The adsorption isotherms of benzene,n-hexane, cyclohexane, and 1,2-dibromo-1,1,2,2-tetrafluoroethane on a nonporous carbon adsorbent, carbon black, were calculated from the results of a gas-chromatographic experiment at 373 K. A general equation of adsorption isotherm for vapors of organic substances on nonporous sorbents that was proposed earlier is shown to be valid in the range of relative pressures,p/p _s, of 10^–7–1 and temperatures of 293–373 K.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1381–1383, August, 1993.     

High resolution N2 adsorption isotherms at 77.4 K and 87.3 K by carbon blacks and activated carbon fibers--analysis of porous texture of activated carbon fibers by αs-method

The standard α(s)-data of N(2) at 87.3 K by graphitized and nongraphitized carbon black samples (GCB-I and NGCB) (cf.Figs. 3 and 4) have been determined on the basis of the high resolution adsorption isotherms of N(2) at 87.3 K, which were repeatedly measured in the pressure range of p/p(o)=5×10(-8)-0.4. The high resolution adsorption isotherms of N(2) by two kinds of activated carbon fibers (ACF-I and ACF-II) were measured from p/p(o)=10(-7) to p/p(o)=0.995 at 77.4 K and from p/p(o)=10(-7) to p/p(o)=0.4 at 87.3 K. Combination of the adsorption isotherms by ACF-I and ACF-II with the standard α(s)-data by NGCB at 77.4 K and 87.3 K make it possible to construct the high resolution α(s)-plots from very low filling (1%) to complete filling (100%). The high resolution α(s)-plots of N(2) at 77.4 K and 87.3 K were analyzed. On the basis of the analyzed result, the porous textures of ACF-I and ACF-II will be discussed.     

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.     

Kinetics of the adsorption of polystyrene macromolecules from dilute solutions in methyl ethyl ketone on carbon black

The kinetics of the adsorption of a mixture of three polystyrenes (the weight-average molecular weight M _w = 8300, 34000, and 195000) on nonporous carbon (carbon black pretreated in the argon flow at 3800 K) from dilute solutions in methyl ethyl ketone at 298 K is studied. The kinetic dependences of the adsorption of polystyrenes on carbon black nanoparticles from solutions in methyl ethyl ketone are described by adsorption kinetics equations previously used for describing the adsorption of aromatic hydrocarbons from aqueous solutions by active carbon. The correlation between the kinetic coefficients and the molecular weights of polystyrenes is discussed.     

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).     

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。     

Carbon black/alumina gel composite: Preparation by sol-gel process in the presence of polymer-grafted carbon black and its electric properties

The preparation of a novel carbon black/alumina gel composite by sol-gel reaction of aluminum isopropoxide (AIP) was investigated. When sol-gel reaction of AIP was carried out in the presence of untreated carbon black, a thin film of alumina gel was hardly obtained, because of the presence of aggregated carbon blacks. On the contrary, in the presence of poly(N-vinyl-2-pyrrolidone)-grafted, poly(2-methyl-2-oxazoline)-grafted, and poly(N,N-diethylacrylamide)-grafted carbon black, a deep-black, thin film of alumina gel, in which carbon blacks were uniformly incorporated, was obtained. Carbon black was incorporated into an alumina gel matrix by the hydrogen bond between carbonyl groups of the grafted polymer and the residual hydroxyl groups in the alumina gel. Electric resistance of the polymer-grafted carbon black/alumina gel composite was very sensitive to the vapor of solvents of the grafted polymer chains on carbon black surface: the electric resistance of the composite drastically decreased in humidity and N,N-dimethylformamide vapor, but not in n-hexane vapor. The logarithm of electric resistance of polymer-grafted carbon black/alumina gel composite linearly decreased in proportion to relative humidity. In addition, the electric resistance of poly(N,N-diethylacrylamide)-grafted carbon black/alumina gel composite under humidity decreased drastically at 32°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3591–3597, 1999     

吸附法脱除乙烯中少量氮气的研究

采用重量法在电子天平上，研究了C2H4和N2单组分在5A、13X、丝光沸石和炭分子筛不同吸附剂上的吸附平衡性质和扩散动力学性质。单柱模拟变压吸附评价了炭分子筛吸附脱除C2H4-N2（N2为4．7％）混合组分中N2的性能，并对流速和压力的影响进行了考察。研究表明，该炭分子筛是吸附脱除C2H4中少量N2的理想吸附剂。     

The influence of intramolecular H-bond on chromatographic behavior of phenylalkylamines

The thermodynamic characteristics of adsorption on the surface of graphitized thermal carbon black at 300 K were determined by the molecular statistical method for three phenylalklylamines. The influence of the intramolecular H-bond on the conformation of the molecules compared with structurally related n-alkyl-benzenes was considered. It was shown that the conformations of the molecules could influence chromatographic retention. Conformational isomers stabilized by intramolecular H-bonds were found to retain their structure in adsorption on graphitized thermal carbon black.     

Synthesis,characterization, and catalytic oxidation of ethylbenzene over host (zeolite-Y)/guest (copper(II) complexes of tetraaza macrocyclic ligands) nanocomposite materials

Cu(II) complexes of 14- and 16-membered tetraaza macrocyclic ligands have been encapsulated in nanopores of zeolite-Y by a two-step process in the liquid phase: (1) adsorption of [bis(diamine)copper(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, and 1,3-diaminobenzene); [Cu(N–N)₂]²⁺–NaY; in the nanopores of the zeolite-Y and (2) in situ condensation of the copper(II) precursor complex with ethylcinnamate. The new host–guest nanocomposite materials were characterized by chemical analysis and spectroscopic methods. The “neat” and encapsulated complexes exhibit good catalytic activity in the oxidation of ethylbenzene at 333 K, using tert-butyl hydroperoxide as the oxidant. Acetophenone was the major product though small amounts of o- and p-hydroxyacetophenones were also formed revealing that C–H bond activation takes place both at benzylic and aromatic ring carbon atoms.     

Comparative analysis of methods for determination of structural characteristics of carbon adsorbents

Experimental data on the equilibrium adsorption of sulfur hexafluoride, methane, carbon dioxide, and benzene on carbon adsorbents of different porosity obtained in a wide pressure range at 298–408 K were analyzed. The adsorption volumes, surface areas, and sizes of slit-shaped pores of the carbons were determined using several independent methods. A method for determination of the adsorption volume from the experimental isotherm of excessive adsorption of gases and the total content equation was proposed. The resulting values are similar to the adsorption volumes calculated from the data for vapors. A new method for the calculation of the adsorbent surface area is described. The method is based on the dependence of the adsorption volume of adsorbent pores on the effective size of adsorbate molecules. A possibility to determine the average size of narrow slit-shaped carbon pores from the difference of the initial heats of adsorption of the gas under study on the carbon black and porous carbon adsorbent is considered. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2219–2227, October, 2005.     

Modeling of adsorption of gases on graphite surfaces accounting for the solid-fluid nonadditivity correction

A series of graphitized carbon blacks have been studied using argon and nitrogen adsorption at their boiling points. Analysis of adsorption isotherms was performed with nonlocal density functional theory (NLDFT) accounting for the Axilrod-Teller equation to describe the effect of nonadditivity of the gas-solid interaction. In our previous study [Ustinov, E. A. J. Chem. Phys. 2010, 132, 194703] we have shown that the nonadditivity effect decreases the attractive component of Ar-Ar interaction in the first molecular layer adjacent to the graphite surface by about 23%. This is a source of a large error (up to 40%) when a standard NLDFT is applied to fitting the low-temperature Ar adsorption isotherm on a graphitized carbon black. A new approach that incorporates the Axilrod-Teller equation into the standard NLDFT diminishes the relative error from 40 to 4%, which suggests that the nonadditivity correction should not be ignored in most adsorption systems including crystalline and amorphous solids. The present study is an extension of our approach to N(2) adsorption isotherms at 77.3 K on graphitized carbon blacks. We show that the approach allows to reliably determine the gas-solid molecular parameters, the gas-solid nonadditivity coefficient, the Henry coefficient, and the specific surface area. The surface areas of different carbon blacks determined with the N(2) at 77.35 K and Ar at 87.29 K are very close to each other, though in the former case the values proved to be slightly smaller presumably due to nonspherical shape of the nitrogen molecule. A comparison with the Brunauer, Emmett, and Teller method is provided.     

Effect of time, temperature, and kinetics on the hysteretic adsorption-desorption of H2, Ar, and N2 in the metal-organic framework Zn2(bpdc)2(bpee)

The intriguing hysteretic adsorption-desorption behavior of certain microporous metal-organic frameworks (MMOFs) has received considerable attention and is often associated with a gate-opening (GO) effect. Here, the hysteretic adsorption of N(2) and Ar to Zn(2)(bpdc)(2)(bpee) (bpdc = 4,4'-biphenyldicarboxylate; bpee = 1,2-bipyridylethene) shows a pronounced effect of allowed experimental time at 77 and 87 K. When the time allowed is on the order of minutes for N(2) at 77 K, no adsorption is observed, whereas times in excess of 60 h is required to achieve appreciable adsorption up to a limiting total coverage. Given sufficient time, the total uptake for N(2) and Ar converged at similar reduced temperatures, but the adsorption of Ar was significantly more rapid than that of N(2), an observation that can be described by activated configurational diffusion. N(2) and Ar both exhibited discontinuous stepped adsorption isotherms with significant hysteresis, features that were dependent upon the allowed time. The uptake of H(2) at 77 K was greater than for both N(2) and Ar but showed no discontinuity in the isotherm, and hysteretic effects were much less pronounced. N(2) and Ar adsorption data can be described by an activated diffusion process, with characteristic times leading to activation energies of 6.7 and 12 kJ/mol. Fits of H(2) adsorption data led to activation energies in the range 2-7 kJ/mol at low coverage and nonactivated diffusion at higher coverage. An alternate concentration-dependent diffusion model is presented to describe the stepwise adsorption behavior, which is observed for N(2) and Ar but not for H(2). Equilibrium is approached very slowly for adsorption to molecularly sized pores at low temperature, and structural change (gate opening), although it may occur, is not required to explain the observations.     

Adsorption properties of iodine-doped activated carbon fiber

Iodine-doped activated carbon fibers (ACFs) were prepared by the iodine immersion method on pitch-based ACF. Then iodine-doped ACFs were heated in argon at 523 K for 4 h and at 673 K for 2 h. The iodine structure of the resultant iodine-doped ACFs was examined using X-ray photoelectron spectroscopy. The micropore structures were determined by N(2) adsorption at 77 K. The surface area and micropore volume of iodine-doped ACFs are less than those of pristine ACFs. However, the pore width does not change with the iodine doping. The effects of iodine doping on adsorption properties of ACFs for H(2)O and NO at 303 K were examined. The iodine doping affected remarkably the adsorptivities of ACFs for H(2)O and NO. In particular, iodine-doped ACFs treated at 673 K show enhanced adsorptivities for H(2)O and NO. This result suggests that iodine molecules doped on the micropores should be charged by heat treatment at 673 K.     

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.     

Surface-modified carbon black for As(V) removal

This paper reports the results of the adsorption performance of As(V) removal by a commercial carbon black and its H2SO4-modified form in a single-ion situation. The influence of different process parameters and the physicochemical principles involved were studied in detail. Acid modification caused morphological changes in the virgin carbon black as evidenced by BET surface area measurements and SEM study. FTIR spectra showed the introduction of sulfonic acid group in the parent carbon due to H2SO4 treatment. TGA analysis revealed higher weight loss characteristics of the modified carbon, demonstrating the creation of functional groups. The point of zero charge (pH pzc) of the modified carbon black is highly acidic (3.5) compared to commercial carbon black (6.4). It directly infers the generation of acidic functional moieties in the carbon black. The adsorption experiments were carried out following batch equilibrium techniques. The kinetics and thermodynamics of adsorption were investigated to unveil the mechanism and nature of the adsorption process, respectively. The kinetic parameters of different models were calculated and discussed. The kinetics of adsorption can be expressed by a pseudo-second-order model and intraparticle diffusion was not the rate-determining step. Dependence of pH on adsorption showed maximum metal uptake in the range of 4-5 and inferred surface complexion as the principal mechanism of adsorption. The equilibrium adsorption data were modeled using Freundlich, Langmuir, and Dubinin-Kaganer-Radushkevich (DKR) isotherm equations and the corresponding isotherm parameters were calculated and discussed in detail.     

Nanoporosities and catalytic activities of Pd-tailored single wall carbon nanohorns

The nanoporosities and catalytic activities of Pd nanoparticles dispersed on single wall carbon nanohorns (Pd-SWCNHs) and oxidized single wall carbon nanohorns (Pd-ox-SWCNHs) were examined. A transmission electron microscopy (TEM) observation indicated that Pd nanoparticles of 2-3 nm size were highly dispersed on both the SWCNHs. X-ray photoelectron spectra and N2 adsorption isotherms at 77 K illustrated the differences in the deposition process mechanisms of the Pd-SWCNHs and Pd-ox-SWCNHs; the deposition process depended on the surface functional groups. The supercritical H2 adsorption isotherms at 77 K suggested the relationships between the interaction of Pd-SWCNHs and Pd-ox-SWCNHs with H2 and the catalytic activities for a water formation reaction in a gas phase at 273 or 298 K. The catalytic activity measurement and TEM observation of the catalysts after the reactions demonstrated that the Pd-SWCNHs and Pd-ox-SWCNHs are promising catalysts.     

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.