Adsorption deformation in the microporous carbon adsorbent-benzene system and porous structure of adsorbents

The relative adsorption deformation of several microporous carbon adsorbents was studied as a function of the benzene adsorption at relative pressure ranging from 1·10⁻¹ to 1.0 and at 293 K. A correlation between the maximum compression of the sample and the characteristic energy of benzene adsorption of the Dubinin-Radushkevich equation was obtained. Using data on the adsorption deformation, it is possible to identify the region with a specific pore size that cannot be evaluated with the help of the Dubinin-Radushkevich equation. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No.6, pp. 1018–1022, June, 2000.     

Adsorption and Thermogravimetric Methods for Monitoring Surface and Structural Changes in Ordered Mesoporous Silicas Induced by their Chemical Modification

The current work demonstrates that the standard adsorption analysis has a limited applicability for characterization of chemically modified porous silicas. Since low-pressure nitrogen adsorption isotherms are sensitive to the surface changes caused by chemical modification of silicas, these isotherms were successfully used to evaluate their surface heterogeneity during different stages of modification. The surface analysis was accomplished by using adsorption energy distributions and high-resolution comparative plots.     

Tailoring Properties of Resol Resin-Derived Spherical Carbons for Adsorption of Phenol from Aqueous Solution

The polycondensation of resorcinol and formaldehyde in a water–ethanol mixture using the adapted Stöber method was used to obtain resol resins. An optimization of synthesis conditions and the use of an appropriate stabilizer (e.g., poly(vinyl alcohol)) resulted in spherical grains. The resins were carbonized in the temperature range of 600–1050 °C and then chemically activated in an aqueous HNO₃ solution, gaseous ammonia, or by an oxidation–reduction cycle (soaking in a HNO₃ solution followed by treatment with NH₃). The obtained carbons were characterized by XRD, the low-temperature adsorption of nitrogen, SEM, TGA, and XPS in order to determine degree of graphitization, porosity, shape and size of particles, and surface composition, respectively. Finally, the materials were tested in phenol adsorption. The pseudo-second order model perfectly described the adsorption kinetics. A clear correlation between the micropore volume and the adsorption capacity was found. The content of graphite domains also had a positive effect on the adsorption properties. On the other hand, the presence of heteroatoms, especially oxygen groups, resulted in the clogging of the pores and a decrease in the amount of adsorbed phenol.     

Pore formation during the pyrolysis of C-Nb2O5 and C-Ta2O5 xerogels

Binary organic-inorganic gels have been prepared by mixing a carbonaceous hydrosol and a Nb₂O₅ or Ta₂O₅ sol derived by hydrolysis of the alkoxides. The gels are pyrolyzed under an inert atmosphere into precursors in which carbon and the metal oxides are mixed very intimately. High temperature treatment converts the precursors into the cubic face centered carbides. The precursors as well as the carbides have been shown to be micro- and mesoporous materials. Measurements of nitrogen adsorption reveal a characteristic change of the shapes of the isotherms (Type I Type IV) and of the hysteresis loops (H4H2H1) during the thermal processes. Pore widening has been observed with rising temperature. The phenomena of crystallization, carbothermal reduction and sintering were found to control the pore shape and size. The results of the adsorption measurement correlate well with those of the thermoanalytical and X-ray diffraction studies.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Design of 2D Porous Coordination Polymers Based on Metallacrown Units

A 12‐metallacrown‐4 (MC) complex was designed and employed as the building block in the synthesis of coordination polymers, one of which is the first permanently porous MC architecture. The connection of the four‐fold symmetric MC subunits by Cu^II nodes led to the formation of 2D layers of metallacrowns. Channels are present in the crystalline architecture, which exhibits permanent porosity manifested in N₂ and CO₂ uptake capacity.     

Effect of Pore Size Distribution and Amination on Adsorption Capacities of Polymeric Adsorbents

Polymeric adsorbents with different properties were synthesized via suspension polymerization. Equilibrium and kinetics experiments were then performed to verify the adsorption capacities of the resins for molecules of various sizes. The adsorption of small molecules reached equilibrium more quickly than the adsorption of large molecules. Furthermore, the resins with small pores are easy to lower their adsorption capacities for large molecules because of the pore blockage effect. After amination, the specific surface areas of the resins decreased. The average pore diameter decreased when the resin was modified with either primary or tertiary amines, but the pore diameter increased when the resin was modified with secondary amines. The phenol adsorption capacities of the amine-modified resins were reduced because of the decreased specific area. The amine-modified resins could more efficiently adsorb reactive brilliant blue 4 owing to the presence of polar functional groups.     

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.     

Physico-chemical characterization of nanofiltration membranes.

This study presents a methodology for an in-depth characterization of six representative commercial nanofiltration membranes. Laboratory-made polyethersulfone membranes are included for reference. Besides the physical characterization [molecular weight cut-off (MWCO), surface charge, roughness and hydrophobicity], the membranes are also studied for their chemical composition [attenuated total reflectance Fourier spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)] and porosity [positron annihilation spectroscopy (PAS)]. The chemical characterization indicates that all membranes are composed of at least two different layers. The presence of an additional third layer is proved and studied for membranes with a polyamide top layer. PAS experiments, in combination with FIB (focused ion beam) images, show that these membranes also have a thinner and a less porous skin layer (upper part of the top layer). In the skin layer, two different pore sizes are observed for all commercial membranes: a pore size of 1.25-1.55 angstroms as well as a pore size of 3.20-3.95 angstroms (both depending on the membrane type). Thus, the pore size distribution in nanofiltration membranes is bimodal, in contrast to the generally accepted log-normal distribution. Although the pore sizes are rather similar for all commercial membranes, their pore volume fraction and hence their porosity differ significantly.     

Adsorption and Mobility of Water and Benzene Molecules in Carbon and Polymer Adsorbents

The correlation between the adsorption and the mobility of adsorbed molecules was analyzed. The peculiarities of molecular mobility in microporous adsorbents with relatively rigid (active carbons) and non-rigid (polymer super-crosslinked and methacrylate sorbents) structure were studied using pulsed nuclear magnetic resonance (NMR) techniques. It was shown that the translational behavior of water and benzene in pores are connected with the specific adsorption mechanism. The NMR data allowed analyzing the changes of molecular state in the processes of adsorption. Diffusional properties of water molecules in the super-crosslinked polystyrenes and active carbons with relatively rigid framework are similar and differ from that in methacrylate polymer sorbents. Moreover, the results of NM relaxation measurements allowed analyzing the porous structure over the scale of pore sizes, while the scale of the self-diffusion measurements comprises the areas of different porosity. The NMR data agree well with the data of adsorption measurements and complement them. Dedication: This work is devoted to memory of the professor W. Schirmer.     

Adsorption of surfactants onto acrylic ester resins with different pore size distribution

In this study, a series of acrylic ester resins with different pore size distribution were prepared successfully by varying the type and the amount of pore-forming agents. In order to inves-tigate the adsorption behavior and mechanism of surfactants on acrylic ester resins, three kinds of surfactants were utilized as adsorbates that were sodium 6-dodecyl benzenesulfonate (6-NaDBS), sodium 1-dodecyl benzene sulfonate (1-NaDBS) and sodium 1-dodecyl sulfonate, respectively. It was observed that the surface area was available in a particular pore size and an appropriate pore size of resins appeared to be more important for the adsorption of surfactants. As compared to commercial acrylic ester resins XAD-7 and HP2MG, 50# and 38# resins exhibited more excellent adsorption properties toward 1-NaDBS and 6-NaDBS. The experimental equilibrium data were fitted to the Langmuir, and double-Langmuir models. Two models provided very good fittings for all resins over the temperature range studied. The investigation indicated that electrostatic attraction and hydrogen bond between resins and surfactants were the main forces and had an obvious effect on adsorption proc-ess.     

Structure Design of Double-Pore Silica and Its Application to HPLC

Utilizing the concurrence of polymerization-induced phase separation and sol-gel transition in the hydrolytic polycondensation of alkoxysilanes, a well-defined macroporous structure is formed in a monolithic wet gel. By exchanging the fluid phase of the wet gel with an appropriate external solution, the nanometer-range structure of the wet gel can be reorganized into structures with larger median pore size essentially without affecting the macroporous framework. The double-pore structure thus prepared is characterized by open pores distributed in discrete size ranges of micrometers and nanometers. A new type of chromatographic column (silica rod) has been developed using monolithic double-pore silica instead of packed spherical gel particles. Typical silica rod columns had significantly reduced pressure drops and improved analytical efficiencies which do not deteriorate even at higher sample flow rates, both arising from a greater macropore volume than particle packed columns.     

Benzene Adsorption Isotherms on MCM-41 and their Use for Pore Size Analysis

This work is focused on the elaboration of methodology for adsorption characterization of porous silicas by using benzene adsorption isotherms measured on good quality MCM-41 materials. Three MCM-41 samples were synthesized by using tetraethyl orthosilicate (TEOS) as silica source and surfactants, octyltrimethylammonium (C8), decyltrimethylammonium (C10) and cetyltrimethylammonium (C16) bromides as templates. A characteristic feature of this synthesis was relatively long hydrothermal treatment (5 days) at 373 K, which gave well ordered samples as evidenced by powder XRD analysis. Benzene adsorption isotherms measured on these MCM-41 samples were used to evaluate such standard quantities as the BET specific surface area, total pore volume, external surface area and the volume of ordered mesopores, and to obtain the statistical film thickness (t-curve) as well as the Kelvin-type relation, which describes the dependence between pore width and condensation pressure for benzene on silica at 298 K. The latter relations were incorporated into the Barrett-Joyner-Halenda algorithm to extend its applicability to calculate the pore size distributions from benzene adsorption data.     

Predicting isotherms in micropores for different molecules and temperatures from a known isotherm by improved Horvath-Kawazoe equations

Our improved Horvath-Kawazoe (H-K) equations (by considering the isotherm nonlinearity) for three pore geometries are first summarized. These equations apply to adsorption in microporous materials at subcritical temperatures. From a known isotherm at a given temperature, these equations are used to predict isotherms of the same adsorbate molecules at other temperatures, and also to predict isotherms for other adsorbate molecules at the same (or any subcritical) temperature. A reasonable agreement is obtained between predictions and experimental data. Since the H-K formulation only involves dispersion forces, it underpredicts for gas-solid systems in which other forces also exist. The N₂-zeolite system is one of these systems.     

表面作用力孔流通模型计算高分子滤过膜孔径大小及分布的方法

综述了一种建立在表面作用力孔流通模型基础上计算高分子多孔滤过膜孔径大小及分布的方法。     

Design and Performance of an Adsorption Bed with Activated Carbons for Biogas Purification

Organic waste can be efficiently converted into energy using highly efficient energy systems, such as SOFCs coupled to the anaerobic digestion process. SOFC systems fed by biogenous fuels, such as biogas or syngas, suffer long-term stability due to trace compound impacts. It follows that, a mandatory gas cleaning section is needed to remove these pollutants at lower concentrations. This work investigates the adsorption mechanism for micro-contaminant removal through experimental results achieved using solid sorbents. Samples of different sorbent materials were analyzed in the laboratory to determine their performances in terms of sulfur (mainly hydrogen sulfide) and siloxanes (mainly D4-Octamethylcyclotetrasiloxane) adsorption capacities. The analysis shows that the chemical composition of the samples influences the adsorption of H₂S (i.e., presence of calcium, iron, copper), while the effect of their textural properties mainly influences the adsorption of siloxane compounds, such as D4. A quantitative analysis was performed considering the influence of gas velocity on adsorption capacity. By increasing the biogas velocity (+45% and +89%), there was an indirect correlation with the H₂S adsorption capacity (−27% and −44%). This identified an aspect related to the residence time required to be able to remove and retain the trace compound. The results obtained and summarized were used to develop a strategy for the removal of trace compounds in large-scale plants, e.g., for water purification.     

利用压差法测定高分辨率超低压吸附等温线的装置

 介绍了一种新型气体吸附测量装置. 该装置利用压差法测量,采用美国MKS高精度压差传感器来提高测量精度,通过微调泄漏阀控制极小进气量,并且采用间断法与连续法相结合. 实验证明,该装置具有很好的可重复性,能获得高分辨率及超低压吸附等温线.     

Numerical Study of Pore Sizes Distribution in Gels

We introduce a new numerical technique for the calculation of the pore size distribution in two-dimensional disordered systems. Our method is based on a triangulation technique which allows a closer measurement of pores surface without any morphological hypothesis.In this work, we focus our calculations in simulated gels. Such materials are modeled in two different conditions: by means of the Diffusion-Limited and Reaction-Limited Cluster-cluster Aggregation algorithms, DLCA and RLCA, respectively. In both situations, when the particles concentration decreases, the average pores size increases. The more compact cluster in RLCA, compared with DLCA, is consistent with the pore size distribution we have calculated. The simulated mean pore size is quantitatively in agreement with experimental data from literature.     

焦化过程半焦孔隙结构时空变化规律的实验研究——孔隙率、比表面积、孔径分布的变化

以井式加热炉(φ150mm×300mm) 为主体模拟工业炼焦过程，借助压汞法考察了焦化过程中不同焦化温度、炉内径向不同位置半焦的孔隙结构参数的变化。结果表明，半焦中存在丰富的大孔和中孔，孔隙率和比表面积随焦化温度、径向位置呈规律性变化；相同焦化温度下，由边缘沿中心方向先减少后增加；相同位置下，孔隙率随着温度的升高逐渐变小，至900℃后孔隙率略有增大，比表面积在900℃左右达到最小值后随温度升高又迅速增加；此外，半焦孔隙以孔径大于5.0μm的孔为主，孔径小于0.4μm、介于0.4μm～5.0μm和大于5.0μm的孔累积孔隙分率分别约占总孔体积分数的10％、20％和70％，孔径分布的高峰处于60 μm～150μm。SEM分析显示，焦柱中存在丰富的大孔，且边缘和中心处孔径较大。     

Adsorption properties of thermally stable and biologically active polyurea: its synthesis and spectral aspects

Novel polymer metal complexes were prepared by the condensation polymerization of a polymeric ligand with transition metal ions of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). The polymeric ligand was prepared by the addition polymerization of urea with toluene 2,4‐diisocyanate in 1:1 molar ratio. The polymeric ligand and its polymer metal complexes were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹³C‐NMR, and¹H‐NMR (nuclear magnetic resonance). The geometry was determined by electronic spectra and magnetic moment measurement. Thermogravimetric analysis (TGA) was utilized to find out the degradation process of the polyurea ligand and the polymer metal complexes. The TGA data revealed that all the metal‐containing polyureas are much more thermally stable than the corresponding polyurea ligand. The surface morphology of the polyurea ligand and cobalt(II)‐containing polyureas was determined by scanning electron micrographs. The antibacterial and antifungal activities of all the synthesized polymers were investigated against Staphylococcus aureus, Escherichia coli, and Bacillus subtilis (bacteria) and Aspergillus niger, Candida albicans, and Aspergillus flavus (fungi). These compounds show remarkably good biocidal activities, which were enhanced after complexation with the metal. Batch adsorption studies of the ligand were carried out for malachite green dye, and the polyurea ligand was found to be a good adsorbent for this dye. Copyright © 2011 John Wiley & Sons, Ltd.     

Validity of energy distribution derived from heat of adsorption in an ammonia/cation-exchanged Y zeolite system

The validity of- functions (energy level functions) which were derived from experimentalq- functions (heat functions) was examined in an ammonia/cation-exchanged Y zeolite system. The- functions of Na-Y zeolite and Cs-Na-Y zeolite were respectively calculated from theirq- functions measured by ammonia adsorption at 373 K. The heat of adsorption of ammonia was also measured on a mixture of these two zeolites at a certain mixing ratio at 373 K. The- function of the mixture was likewise calculated on the basis of this measurement. The- function thus calculated was in good agreement with the synthesized- function derived by linearly combining two- functions of each zeolite mentioned above. The- function derived from experimental- function thus proved to be valid in an actual adsorption system.