Structure and property of the hydrogen bonding complex between triazines and water

The study of the intermolecular interactions that drive the solvation of six-membered nitrogenated aromatic rings is of particular importance since they are known to constitute key building blocks of pro- teins and nucleotides[1―5]. The investigation of the 1:1 adduct of these molecules with water will be the first step in the understanding of such interactions. These molecules possess two different proton-acceptor sites: the ring π cloud and the lone pairs of electrons on the nitrogen atoms…     

Role of the surface heterogeneity in adsorption of hydrogen ions on metal oxides: theory and simulations

In this article we study the effect of energetic heterogeneity of a crystalline surface on the adsorption of hydrogen ions (protons) from the liquid phase. In particular, we examine the influence of the shape of the adsorption energy distribution on the equilibrium isotherms of hydrogen ions. To that purpose, a few popular distribution functions, including rectangular, exponential, and asymmetric Gaussian are considered. Additionally, multimodal distribution functions, which may correspond to the adsorption on different crystal planes of the oxide, are also used. Lateral interactions between adsorbed charges are modeled using the potential function proposed by Borkovec et al., which accounts also for polarization of the liquid medium. The results presented here are obtained using both Monte Carlo (MC) simulations and theoretical calculations involving Mean Field Approximation (MFA). They indicate that increased energetic heterogeneity of the adsorbing surface may, in general, considerably change the behavior of the adsorption isotherms, regardless of the assumed distribution function. It is also shown that the predictions of the proposed theory are consistent with the data obtained from the MC simulations.     

Analysis of the Micropore Structure of Various Microporous Materials from Nitrogen Adsorption at 77 K

The micropore structure of four microporous materials (two zeolites, ZSM-5 and Y-82; an activated carbon and an alumina pillared clay) and their binary physical mixtures (50-50 wt%) have been examined by nitrogen adsorption at 77 K. Various micropore sizes have been considered from the stages on the micropore filling mechanism in the microporous materials. The application of the Dubinin-Astakhov (DA) equation to characterize and obtain the adsorption potential distributions of the microporous materials is presented.     

A simple isotherm equation for describing gas adsorption on heterogeneous microporous solids

A simple isotherm equation for describing gas adsorption on solids showing heterogeneity of microporous structure is proposed. It is shown that this equation gives a good representation of the experimental data of argon, nitrogen and benzene adsorption on different types of activated carbons. Its parameters may be used to characterize heterogeneity of microporous structure of the solids.

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Eine einfache Isotherme zur Beschreibung der Gas-Adsorption an heterogenen mikroporösen Feststoffen

Zusammenfassung Es wird eine einfache Isotherme zur Beschreibung der Gasadsorption an Feststoffen mit heterogener mikroporöser Struktur vorgeschlagen. Es wird gezeigt, daß diese Gleichung die experimentellen Daten für die Adsorption von Argon, Stickstoff und Benzol an verschiedenen Typen von Aktivkohle gut beschreibt. Die Parameter der Isotherme können zur Charakterisierung der Heterogenität der mikroporösen Struktur von Festkörpern herangezogen werden.

     

Modification of solids with volatile organics III: Natural zeolites

Summary The effect of pre-adsorbed benzene and ethanol on the adsorptive properties of natural zeolite (clinoptilolite) has been studied by gas-solid chromatography. It has been shown that modification of the solid surface by volatile organics has a significant influence on the adsorptive properties. The modification is of the same order as the more difficult modification by inorganics, as illustrated here by clinoptilolite modification with Co²⁺. Energy distribution of surface adsorptive sites appears to be continuous and confirms previous finding that only a small proportion of active sites is responsible for most adsorbate retention. Part II reference [4]     

IR study of heterogeneity of OH groups in zeolite HY-splitting of OH and OD bands

We have been studying the problem of heterogeneity of OH groups in zeolites HY for a long time. The heterogeneity was suggested by the shift of the IR band of OH groups restoring upon ammonia desorption and also by the fact that the band of OH groups forming hydrogen bonds was relatively broad (broader than for homogeneous acidic OH). In the present study we present another important argument for heterogeneity: the splitting of the IR band of free OH and OD groups in a zeolite of Si/Al=8.3 dealuminated by (NH₄)₂SiF₆ treatment. Such a splitting is the best seen in low temperature spectra of OD groups. We found less acidic 3640 cm⁻¹ (AlO)(SiO)₂SiO₁HAl(OSi)₃ and more acidic 3625 cm⁻¹ (SiO)₃SiO₁HAl(OSi)₃ groups. The presence of these two kinds of hydroxyls corresponds to the presence of Si(2Al) and Si(1Al), respectively, detected in ²⁹Si MAS NMR spectra. We also found a small amount of strongly acidic 3599 cm⁻¹ hydroxyls interacting with extraframework Al species.     

阴离子嵌段共聚的交联聚苯乙烯的网络链长多分散性与网络结构非均一性

用链长分布不同的活性聚苯乙烯子聚物与二乙烯基苯进行阴离子嵌段共聚,合成了一系列两相模型交联网络。以作者等提出的方法测定了所合成网络的结构非均一因子Z。实验测定的网络结构非均一因子Z与交联前聚苯乙烯活性链的分子量分布宽度指数d之间有平行的相应变化规律,表明所给予的非均一因子Z的物理意义是合理的。同时说明,子聚物链长分布较宽时,在网络的高交联区中除了二乙烯基苯外,还有一些对溶胀无贡献的子聚物以悬挂链的形式存在。     

Studies of surface properties of Na- and La-montmorillonites

This paper presents possible applications of thermal analysis, sorptometry and porosimetry to study physico-chemical properties of Na- and La-montmorillonite samples, especially for determination of total surface heterogeneity. The quasi-isothermal thermogravimetric (Q-TG) mass loss and its first derivative (Q-DTG) curves with respect to temperature and time obtained during programmed liquid thermodesorption under quasi-isothermal conditions have been used to study adsorbed layers and heterogeneous properties of the Na- and La-montmorillonites. Calculations of the desorption energy distribution functions by analytical procedure using mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption under quasi-isothermal conditions of polar and non-polar liquid vapours preadsorbed on a material surface are presented. Parameters relating to porosity of samples were determined by sorptometry, mercury porosimetry and atomic force microscopy (AFM). From nitrogen sorption isotherms from sorptometry and porosimetry methods, the fractal dimensions of montmorillonites have been calculated. Moreover, a new approach is proposed to calculate fractal dimensions of materials obtained from Q-TG curve; this is compared with values obtained by the above methods. The total heterogeneous properties (energy distribution function and pore-size distribution functions) of samples studied were estimated. The radius and pore volume of the tested samples calculated on the basis of thermogravimetry, sorptometry and porosimetry techniques were compared and good correlations obtained.     

Controlled-rate thermal analysis

Controlled-rate thermal analysis (CRTA) and differential scanning calorimetry (DSC) were used to investigate the adsorbed water layers and the surface properties of different commercial activated carbons. A simple method is proposed to obtain information on the properties of the adsorbed water film and the surface heterogeneity of the materials studied. This method utilizes TG mass loss and the first derivative of the DTG mass loss curves with respect to temperature and time, obtained during programmed liquid thermodesorption. The obtained TG mass loss curves, which reflect the energetic heterogeneity, consisted of steps and inflections which were associated with the mechanism of wetting of the solid surfaces. The heights of these steps and inflections depend on the adsorption capacity, the adsorption potential and the nature and number of the active centers of the carbon samples studied. The values of the total porosity and the surface phase capacity obtained by this method are in good agreement with those estimated on the basis of independent methods. The behaviour of water/carbon samples was studied by means of DSC at subambient and elevated temperatures. The experimental results provided novel data on the structural heterogeneity, the thermal stability of the water/carbon interface and its phase and structural transitions.Support from the Research Council of Kent State University (Ohio, USA) is acknowledged. The author is pleased to thank Drs M. Jaroniec, R. K. Gilpin, J. Choma and R. Dobrowolski for fruitful discussions and the active carbon samples.     

Determination of total heterogeneity and fractal dimensions of high-temperature superconductors

Using thermo-analytical and sorptometric methods physicochemical properties and especially surface heterogeneity of HgBa₂Ca₂Cu₃O₈₊, (Hg-1223) was investigated. The desorption energy distribution was derived from mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption in quasi-isothermal conditions of pre-adsorbed n-octane and water vapour. It is shown that the superconducting Hg-1223 phase is highly sensitive to water vapours. The mechanism of water adsorption depends largely on the activation time. By water vapour saturation in a period of 90 min, physisorption takes place. Prolonged periods result in a chemical decomposition. From nitrogen ad- and desorption isotherms the fractal dimension of superconductors were calculated. A new approach is proposed to calculate fractal dimension from Q-TG curves.This revised version was published online in November 2005 with corrections to the Cover Date.