Structural features of polymer adsorbent LiChrolut EN and interfacial behavior of water and water/organic mixtures

The structural and adsorption characteristics of polymer adsorbent LiChrolut EN and the behavior of adsorbed water and water/organic mixtures were studied using adsorption, microcalorimetry, transmission and scanning electron microscopy, mass spectrometry, infrared spectroscopy, 1H NMR spectroscopy with layer-by-layer freezing-out of liquids (190-273 K), and thermally stimulated depolarization current method (90-265 K). This adsorbent is characterized by large specific surface area (approximately 1500 m2/g) and pore volume (0.83 cm3/g) with a major contribution of narrow pores (R<10 nm) of a complicated shape (long hysteresis loop is in nitrogen adsorption-desorption isotherm). The adsorbent includes aromatic and aliphatic structures and oxygen-containing functionalities and can effectively adsorb organics and water/organic mixtures. On co-adsorption of water and organics (dimethyl sulfoxide, chloroform, methane), there is a weak influence of one on another adsorbate due to their poor mixing in pores. Weakly polar chloroform displaces a fraction of water from narrow pores. These effects can explain high efficiency of the adsorbent in solid-phase extraction of organics from aqueous solutions. The influence of structural features of several carbon and polymer adsorbents on adsorbed nitrogen, water and water/organics is compared on the basis of the adsorption and 1H NMR data.     

Structural and energetic properties of carbosils hydrothermally treated in the classical autoclave or the microwave reactor

Carbon/silica adsorbents (carbosils) prepared by pyrolysis of CH₂Cl₂ at 823 K and the reaction time from 0.5 to 6 h on the mesoporous silica gel surface (Si-60, Merck, granule size 0.2–0.5 mm) and then hydrothermally treated at 473 K with steam or liquid water by using the classical autoclave with traditional heating way or in the microwave reactor were studied by means of TG, adsorption and Q-TG methods. Changes in the structural characteristics of hybrid adsorbents before and after hydrothermal treatment were analyzed on the basis of nitrogen adsorption. Thermal properties of initial and modified samples as well as concentration of carbon deposit were studied using thermogravimetry (TG) in the range of 293–1273 K. The adsorbed water layers were investigated by means of thermodesorption of water under the quasi-isothermal conditions (Q-TG) in the range of 293–573 K. Concentration of weakly and strongly adsorbed water and the surface free energy on the interphase of adsorbent/water were calculated. It was stated that hydrothermal treatment in the microwave reactor, contrary to that in the classical autoclave, allows to obtain adsorbents with noticeably higher values of total pore volume in relation to the initial adsorbents and in majority with a higher specific surface area. Application of microwave energy allows to obtain adsorbents with lower values of surface free energy in relation to the initial adsorbents and those modified in the autoclave.     

Structural and Energetic Nonuniformities of Pyrocarbon-Mineral Adsorbents

Several series of pyrocarbon-mineral adsorbents (carbosils) were studied using the nitrogen adsorption method to compute structural and energetic parameters within the scope of overall adsorption isotherm approximation applying a regularization procedure with consideration for surface heterogeneity. A portion of pyrocarbon deposits (graphene clusters) fills mesopores of the oxide supports, but another portion represents relatively large nonporous pyrocarbon globules formed on the outer surfaces of the oxide matrices. Contributions of these two types of pyrocarbon deposits depend on the nature of oxide matrices and carbonized precursors. The characteristics of pyrocarbon formed on the silica (silica gel, fumed silica) surfaces differ from those for deposits prepared on the surfaces of titania/silica and alumina/silica or by the pyrolysis of metal acetylacetonates (Zr(AcAc)(4), TiO(AcAc)(2), Ni(AcAc)(2), Zn(AcAc)(2), Cr(AcAc)(3), Co(AcAc)(2)) on mesoporous silica gel. The structural and energetic characteristics estimated using the adsorption method with consideration for the adsorbent heterogeneity are fruitful for comparative analysis of the (1)H NMR spectra of water adsorbed on carbosils from the gas phase or unfrozen in the aqueous suspensions at T < 273 K. Copyright 2001 Academic Press.     

Characteristics of interfacial water affected by proteins adsorbed on activated carbon

The influence of proteins (bovine serum albumin, BSA, and mouse gamma-globulin, IgG) physically adsorbed or covalently attached via coupling with N-cyclohexyl-N'-(2-morpholinoethyl) carbodiimide methyl-p-toluenesulfonate, CMC, to the surface of activated carbon SCN (spherical carbon with nitrogen) on the mobility of interfacial water molecules was studied by means of 1H NMR spectroscopy with freezing-out of bulk water at 180 < T < 273 K. Relaxation processes in the interfacial non-freezing water were investigated measuring transverse time t2 of proton relaxation dependence on the presence of proteins and CMC. The distribution function of activation free energy of relaxation (with a maximum at 20-22 kJ/mol) was calculated for the protein-water-carbon systems using a regularization procedure and the relationships between t2 and the amounts of the interfacial water unfrozen at T < 250 K assuming the Arrhenius-type dependence for t2(-1) on temperature. The state of unfrozen water in pores of SCN shows that the low temperature relaxation processes occur in narrow pores with half-width X < 1.5 nm.     

Influence of organics on the structure of water adsorbed on activated carbons

The influence of organics on the structure of water adsorbed on activated carbons was studied using adsorption of nitrogen, benzene, and water, and by (1)H NMR spectroscopy with freezing out of bulk water with the presence of benzene-d(6) or chloroform-d. It was found that interactions of water with the activated carbon surface depend on both structural characteristics (contributions of micro- and mesopores, pore size distributions) of adsorbents and chemical properties (changed by oxidation or reduction) of the adsorbents. Moreover, the interfacial behavior of water is affected by water-insoluble organics such as benzene and chloroform. Changes in the Gibbs free energy of water adsorbed on carbons exposed to air, water, chloroform-d, or benzene-d(6) are related to textural properties of adsorbents and the degree of their oxidation. Since chloroform-d and benzene-d(6) are strongly adsorbed on activated carbons and immiscible with water they replace a significant portion of adsorbed water in micropores, on the walls of mesopores, and in the transport pores of carbons causing changes in the Gibbs free energy and other characteristics of water.     

Changes in the morphology of interstellar ice analogues after hydrogen atom exposure

The morphology of water ice in the interstellar medium is still an open question. Although accretion of gaseous water could not be the only possible origin of the observed icy mantles covering dust grains in cold molecular clouds, it is well known that water accreted from the gas phase on surfaces kept at 10 K forms ice films that exhibit a very high porosity. It is also known that in the dark clouds H(2) formation occurs on the icy surface of dust grains and that part of the energy (4.48 eV) released when adsorbed atoms react to form H(2) is deposited in the ice. The experimental study described in the present work focuses on how relevant changes of the ice morphology result from atomic hydrogen exposure and subsequent recombination. Using the temperature-programmed desorption (TPD) technique and a method of inversion analysis of TPD spectra, we show that there is an exponential decrease in the porosity of the amorphous water ice sample following D-atom irradiation. This decrease is inversely proportional to the thickness of the ice and has a value of ?(0) = 2 × 10(16) D-atoms cm(-2) per layer of H(2)O. We also use a model which confirms that the binding sites on the porous ice are destroyed regardless of their energy depth, and that the reduction of the porosity corresponds in fact to a reduction of the effective area. This reduction appears to be compatible with the fraction of D(2) formation energy transferred to the porous ice network. Under interstellar conditions, this effect is likely to be efficient and, together with other compaction processes, provides a good argument to believe that interstellar ice is amorphous and non-porous.     

DFT investigation of NH3 physisorption on CuSO4 impregnated SiO2

In this quantum chemical investigation, NH(3) physisorption onto a model of copper sulfate impregnated silica is compared with pure silica and copper sulfate adsorbents. The physisorption process is modeled as direct binding of the NH(3) molecule to the adsorption site of the dry adsorbents and as displacement of a H(2)O molecule by NH(3) in the hydrated complexes. The surface of silica is represented by a hydroxyl group attached to a silsesquioxane cage, H(7)Si(8)O(12)(OH) and silica impregnated with CuSO(4) by the most stable configuration of the cluster containing a CuSO(4) ion pair placed adjacent to the silica cage. H(2)O is systematically added to the dehydrated adsorbents to investigate the role of water in NH(3) adsorption. Modeling hydrated environments of each type of adsorbent is focused on H(2)O molecules that directly coordinate with the active sites. The results indicate that the binding energy of adsorbing NH(3) onto the mixed adsorbent is greater than in pure silica. This enhanced binding in the mixed adsorbent is consistent with improved Br?nsted acidity of the silanol in the presence of CuSO(4).     

用固体~1H MAS NMR研究水在不同吸附质中的状态

应用固体1H MAS NMR实验技术,根据核磁共振峰线宽的不同,表征了水在不同吸附质中的微观状态。在含水的壳聚糖和明胶中,以氢键形式存在的水的共振峰线宽为2000Hz左右。在含水分子筛和含水硅胶中存在的吸附水的共振峰线宽在1000Hz左右。而自由水的核磁共振峰线宽小于3Hz。     

Preparation and modification of complex pyrolytic carbon-silica adsorbents

Summary The surface properties of complex adsorbents prepared through the pyrolysis of dichloromethane on the surface of silica gel were investigated. The reaction was carried out in a specially constructed reactor at 400–500°C. The construction and performance of the reactor are described. The modification of the silica gel surface by pyrogenic carbon results in its chemical but not energetical homogeneity. Such adsorbents usually show strong adsorptive properties which limits their use in chromatography. A simple method of homogenizing the porous structure and energetic properties of the adsorptive centers of such adsorbents is presented. The method consists of an additional pyrolysis of an alcohol or other substances on the surface of the carbon-silica adsorbent. Such reactions were carried out under both static and dynamic conditions. The properties of the modified adsorbent depend on the reaction conditions and on the type of the additionally pyrolysed substance.     

Structural and Adsorptive Characteristics of Pyrocarbon/Silica Gel Si-60

Pyrocarbon/silica gel adsorbents (carbosils, CS) with mesoporous Si-60 (Merck, granule size 0.2–0.5 mm) modified by pyrolysis of CH₂Cl₂ at 823 K and reaction time from 0.5 to 6 h and then hydrothermally treated at 473 K for 6 h were studied by means of TEM, adsorption and ¹H NMR methods. Changes in the structural and adsorptive characteristics of hybrid adsorbents before and after hydrothermal treatment, which depend on pyrocarbon content (C _C), were analyzed on the basis of TEM micrographs and p-nitrophenol and nitrogen adsorption isotherms treated using a constrained regularization method. Interfacial water layers in aqueous suspension of CS were investigated by means of ¹H NMR with freezing-out of bulk water at T < 273 K showing nonlinear changes in the Gibbs free energy of interfacial water with increasing C _C because of nonlinear dependence of the structural characteristics of pyrocarbon deposits and CS as a whole on C _C.     

Effect of chemical modification on carbon dioxide adsorption property of mesoporous silica

Three adsorbents were prepared by different modification methods, which were grafting silica gel with (3-aminopropyl) trimethoxysilane, grafting silica gel with acrylamide polymer, and impregnating silica gel with acrylamide polymer, respectively. The characterization of materials was carried out by N(2) adsorption experiments, Fourier transform infrared spectroscopy, scanning electron microscopy, thermo-gravimetric analysis, and elemental analyses. The results showed that the amine group was successfully loaded on all three modified adsorbents; among that, the polymer-modified silica adsorbents had higher amine content and larger surface area than the aminopropyl-grafted silica adsorbent and displayed higher thermal stability than the other polymer-modified silica materials previously reported. The CO(2) adsorption/desorption experiments performed at 25°C by TGA-DSC method showed that the highest CO(2) adsorption capacity (0.98 mmol/g) was observed for the polymer-impregnated silica adsorbent. CO(2) adsorbed on all samples was completely desorbed by purging with inert gas at 60°C except for the aminopropyl-grafted silica material, which showed the highest enthalpy of CO(2) adsorption.     

Impedance Spectroscopic Measurements of Pure Gas Adsorption Equilibria on Zeolites

Physisorption equilibria of gases on inert porous solids like activated carbon or molecular sieves can be characterized by measuring the (frequency dependent) capacitance of a capacitor filled with a sample adsorbent. This quantity strongly depends not only on the physico-chemical structure of the empty adsorbent in vacuum, but also on the permanent or induced dipole moments of the molecules adsorbed and of the fluid phase. Consequently, it should be possible to determine the excess mass being adsorbed on the internal surface of a highly porous solid by measurements of the dielectric constant. The aim of this work is to show for various pure gases and adsorbents that the change of the capacitance of an adsorption system depends on the adsorbed mass. Therefore, this effect can be used to characterize porous solids and their adsorbates and, for example, to check the state or the quality of industrial adsorbents during a process on site if calibration measurements have been taken (Staudt et al., 1994, 1998).     

Estimation of the energetic nonhomogeneity of the surface of oxide and carbon materials

The molecular statistical method for evaluating the distribution of active sites of various adsorbents relative to their energies has been improved. This method is used not only for the treatment of experimental data on the adsorption of hydrocarbons on various adsorbents, which is the usual procedure, but also data on the adsorption of polar water and methanol molecules on the active sites of adsorbent surfaces. Two types of active sites differing in energy have been shown to exist on the surface of graphitized carbon black, the complex shungite carbon/mineral adsorbent, and modified Silochrom. Chromatographic, calorimetric, and structural adsorption data were used to establish the relationship between the observed maxima of the energy distribution function of the adsorption sites with concrete adsorption sites or pores of the surface, on which the molecules are adsorbed. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 44, No. 5, pp. 315–320, September–October, 2008.     

Comments on the size of the adsorbed phase in porous adsorbents

An alternative to the conventional ‘pore filling model’ for describing Gibbsian surface excess (GSE) isotherm from a liquid mixture on a porous adsorbent is proposed where the adsorbed phase volume is treated as a variable. The new model is tested using GSE isotherm data on various micro and mesoporous adsorbents. The adsorbed phase volume is found to be system specific but always less than the adsorbent pore volume, irrespective of the pore size.     

Adsorption and calorimetric studies of hydrothermally modified carbosils

The article presents the studies of effects of hydrothermal treatment (HTT) (in saturated water vapours or under the liquid water layer) using various sources of thermal energy (classical autoclave or high pressure microwave reactor) on structural and surface properties of initial and modified silica gels and carbon–silica adsorbents. The porous structure of the initial and modified materials was characterised by the low-temperature nitrogen adsorption/desorption method as well as by determining pore volume distribution curves from the calorimetric data (DSC) using the thermal effects of liquid (water) phase transitions previously brought inside the pores of the studied materials. Large compatibility of the characteristics obtained using the above methods was found. The microscopic investigations (SEM, TEM) were also conducted to evaluate the morphology and topography of the samples. It was proved that during HTT, the carbon deposit on the silica surface screens it against the access of water molecules, in this way affecting decrease in intensity of dissolution and condensation of polysilicic acids. At the same time, owing to oxidizing properties of water molecules under hydrothermal conditions, development of porous structure in the carbon deposit is observed. Extent of these changes depends on both the applied system (water vapour/liquid water) and kind of the used energy (classical/microwave).     

Complex investigations of structural and thermal properties of silica-titania adsorbents

Mesoporous titanium-containing silicas with different Titania contents were investigated. The structural parameters of the materials were characterized by low-temperature adsorption/desorption of nitrogen and X-ray diffraction analysis. The thermodesorption of water using the quasi-isothermal thermogravimetry as well as the differential scanning calorimetry were used to characterize thermal and surface properties of these materials. The adsorbed water layers and the concentration of weakly and strongly bound water as well as the surface free energy on the adsorbent/water interfaces were calculated. It was stated that the increase of Titania content causes a gradual decrease of specific surface area and formation of biporous structure inside the tested materials. The water thermodesorption from the surface proceeds in two or three stages, which is connected mainly with pore distribution and TiO₂ content. One can observe the increase of the total surface free energy (??G _??) with the increasing TiO₂ content, but the largest ??G _?? value at the adsorbent/strongly bound water interface is exhibited by the adsorbent of intermediate content (30%) of TiO₂. Freezing temperature of water contained in the pores of the studied materials is connected largely with their porous structure. Due to the well developed porous structure, the water freezing process is a multi-stage one.     

State of water in amorphous silica samples from rice hulls: A <Superscript>1</Superscript>H NMR study

Behavior of molecules of adsorbed water in rice hulls, weevil, and amorphous samples of carbon-containing (carbonized, SiO₂ content 47%) and pure silica was studied by ¹H NMR spectroscopy in the temperature range from 200 to 298 K. The temperature dependence of the signal intensity from humid samples shows a decrease in temperature of freezing of the adsorbed water and presence of unfrozen water. This dependence was used for estimating the pore size distribution. For pure amorphous silica, the pore diameter is in the range from 50 to 150 Å with a maximum at about 85 Å.     

Preparation of complex carbon-silica adsorbents with different properties

Summary The surface properties of complex adsorbents prepared through the pyrolysis of benzyl and n-heptyl alcohols and their mixtures on the surface of silica gel were investigated. The reactions were carried out in an autoclave at 500°C. A series of adsorbents having different porous structure, chemical nature of the adsorption centers and their topography were obtained. The best resolution of different mixtures was obtained by the carbon-silica adsorbent prepared through the pyrolysis of n-heptanol.     

Porous structure of rigid and swelling adsorbents according to pulsed NMR data on the mobility of adsorbed water and benzene molecules

Potentialities of pulsed NMR technique to estimate parameters of the porous structure of microporous adsorbents according to the data on nuclear magnetic relaxation and self-diffusion of adsorbed molecules are analyzed. Main attention was focused on the adsorbed systems studied by the adsorption and NMR techniques. Measurements of nuclear magnetic relaxation of adsorbed molecules make it possible to analyze the porous structure at the scale of pore sizes; data on self-diffusion, at the scale of different-porosity zones. Specific features of the translational mobility of water and benzene molecules with different mechanisms of adsorption in active carbons having relatively rigid structure and polymer adsorbents capable of swelling are discussed. In general, data obtained by the NMR technique agree with and supplement the results of adsorption measurements.     

Adsorption and catalytic properties of peroxidase

The adsorption of peroxidase was studied on ten silicate adsorbents, aluminosilicate, and alumina. It was shown that its value depended on both the parameters of the porous structure and the nature of the adsorbent. The maximum adsorption values were obtained on biporous silicate adsorbents and biporous aluminosilicate. It was established that the adsorbed peroxidase layers on these adsorbents had the best catalytic properties as well. It was shown that the specific activity of the enzyme depended on the degree of the surface filling.