Dubinin's theory and its contribution to adsorption science
2001, Stoeckli, Fritz
Dubinin's theory for the volume filling of micropores (TVFM), originally developed for the adsorption of single vapours by microporous solids such as activated carbons and Zeolites, has gradually been extended to other areas. They include immersion calorimetry, the adsorption of water vapour and of mixtures, as well as adsorption front aqueous solutions. Recent studies in the field of adsorption from aqueous solutions, by activated carbons, suggest that the principle of temperature invariance is fulfilled and in the case of phenolic compounds a modified DRK equation can be used to predict the adsorption equilibrium over a certain range of temperatures. Computer modelling of CO2 adsorption by carbons at 273 K leads to micropore distributions, which are in good agreement with those derived from other techniques. It also appears that the model isotherm, in single slit-shaped micropores can be fitted to the Hill-de Boer isotherm, in agreement with mathematical studies of the origin of the Dubinin-Astakhov equation.
On the mechanisms of phenol adsorption by carbons
2001, Stoeckli, Fritz, Hugi-Cleary, D.
The removal of phenol and related compounds from dilute aqueous solutions by activated carbons corresponds to the coating of the micropore walls and of the external surface by a monolayer. This process is described by an analog of the Dubinin—Radushkevich—Kaganer equation. On the other hand, as suggested by immersion calorimetry at 293 K, in the case of concentrated solutions, the mechanism corresponds to the volume filling of the micropores, as observed for the adsorption of phenol from the vapor phase. The equilibrium is described by the Dubinin—Astakhov equation. It follows that the removal of phenol from mixtures with water depends on the relative concentrations, and the limiting factor for adsorption is either the effective surface area of the carbon, or the micropore volume.
On the determination of surface areas in activated carbons
2005, Stoeckli, Fritz, Centeno, Teresa A.
The paper examines the validity of two approaches frequently used to determine surface areas in activated carbons, namely the BET method and the use of immersion calorimetry. The study is based on 21 well characterized carbons, whose external and microporous surface areas, Se and Smi, have been determined by a variety of independent techniques. It appears clearly that SBET and the real surface area Smi + Se are in agreement only for carbons with average pore widths Lo around 0.8–1.1 nm. Beyond, SBET increases rapidly and SBET− Se is practically the monolayer equivalent of the micropore volume Wo. This confirms that a characterization of surface properties based on SBET is, a priori, not reliable. The study of the enthalpy of immersion of the carbons into benzene at 293 K, based on Dubinin’s theory, shows that ΔiH consists of three contributions, namely from the interactions with the micropore walls (−0.136 J m−2), the external surface (−0.114 J m−2), and from the volume W*o of liquid found between the surface layers in the micropores (−141 J cm−3). It appears that for carbons where Lo> 1 nm, the real surface area cannot be determined in a reliable way from the enthalpy of immersion and a specific heat of wetting alone.
Characterization of industrial activated carbons by adsorption and immersion techniques and by STM
1995, Stoeckli, Fritz, Centeno, Teresa A., Donnet, Jean-Baptiste, Pusset, Nadia, Papirer, Eugéne
The results obtained from a variety of techniques (vapour adsorption, selective adsorption of caffeine and immersion calorimetry) used to characterize activated carbons of industrial origin are compared. It is shown that gate effects due to constrictions, and often overlooked, can be revealed by simple experiments with larger molecular probles. Immersion calorimetry appears to be a simple and efficient technique, as illustrated by an activation series. Complementary information is also provided by scanning tunnelling microscopy (STM).
The effect of the carbonization/activation procedure on the microporous texture of the subsequent chars and active carbons
2003, Cagnon, Benoît, Py, Xavier, Guillot, André, Stoeckli, Fritz
Chars obtained by carbonizing coconut shells at different intermediate heat treatment temperatures (IHTT) between 400 and 800 °C were activated at 800 °C in a stream of N2+H2O, following two distinct procedures. In the first procedure, activation follows directly the carbonization, whereas in the second procedure, the sample was first brought back to 25 °C and subsequently heated again to the activation temperature of 800 °C. The data for CO2 adsorption at 25 °C and N2 at −196 °C with immersion calorimetry confirms that the activated carbons derived from chars obtained at low IHTT and in two steps, present a “gate effect” for burn-offs <20% or 25%, otherwise, the final carbons present similar structural characteristics for higher burn-offs. It also appears that the evolution of the average pore width L0 with the micropore volume W0 follows a general pattern outlined early.