No abstract

MIL-101, a chromium-based metal organic framework, is known to adsorb large amounts of green house gases such as CO 2 and CH 4 . Measurement, analysis, and modeling of the pure gas adsorption isotherms of desired gases are necessary for any attempt to use this framework for separation/storage applications. In an attempt to understand adsorption characteristics of this framework, pure gas adsorption properties of CO 2 and CH 4 along with C 3 H 8 , SF 6 , and Ar were measured at three temperatures 283, 319, and 351 K using a standard gravimetric method. The adsorbates were chosen based on their physical characteristics such as polarizability and quadrupole moment. Dual site Langmuir (DSL) isotherm proved to be useful for modeling adsorption of gases on this type of materials that are known to have heterogeneity. Active metal centers and sites inside the pores of supertetrahedra act as major locations for adsorption. Analysis of enthalpy of adsorption using the DSL model revealed that, for all gases, it initially decreases with loading and remains constant thereafter. For all gases considered, the enthalpies of adsorption were found to be lower than those on purely siliceous zeolite such as silicalite, suggesting that only moderate interaction exists between the gas and the MIL-101 framework. The enthalpy of adsorption at zero coverage and the logarithm of Henry's constant were found to be linear functions of polarizability of the adsorbate.

No abstract

The thermodynamic treatment of adsorption phenomena is based on the Gibbs dividing surface, which is conceptually clear for a flat surface. On a flat surface, the primary extensive property is the area of the solid. As applications became more significant, necessitating microporous solids, early researchers such as McBain and Coolidge implemented the Gibbs definition by invoking a reference state for microporous solids. The mass of solid is used as a primary extensive property because surface area loses its physical meaning for microporous solids. A reference state is used to fix the hypothetical hyperdividing surface typically using helium as a probe molecule, resulting in the commonly used excess adsorption; experimentalists measure this reference state for each new sample. Molecular simulations, however, provide absolute adsorption. Theoreticians perform helium simulations to convert absolute to excess adsorption, mimicking experiments for comparison. This current structure of adsorption thermodynamics is rigorous (if the conditions for reference state helium measurements are completely disclosed) but laborious. In addition, many studies show that helium, or any other probe molecule for that matter, does adsorb, albeit to a small extent. We propose a novel thermodynamic framework, net adsorption, which completely circumvents the use of probe molecules to fix the reference state for each microporous sample. Using net adsorption, experimentalists calibrate their apparatus only once without any sample in the system. Theoreticians can directly calculate net adsorption; no additional simulations with a probe gas are necessary. Net adsorption also provides a direct indication of the density enhancement achieved (by using an adsorbent) over simple compression for gas (e.g., hydrogen) storage applications.

No abstract