Investigating cluster formation in adsorption of CO2, CH4 and Ar in zeolites and metal organic frameworks at subcritical temperatures

Krishna, Rajamani ; van Baten, Jasper M. (2010) Investigating cluster formation in adsorption of CO2, CH4 and Ar in zeolites and metal organic frameworks at subcritical temperatures Langmuir, 26 (6). pp. 3981-3992. ISSN 0743-7463

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Official URL: http://pubs.acs.org/doi/abs/10.1021/la9033639

Related URL: http://dx.doi.org/10.1021/la9033639

Abstract

The critical temperatures, Tc, of CO2, CH4 and Ar are 304 K, 191 K and 151 K, respectively. This paper highlights some unusual characteristics of adsorption and diffusion of these molecules in microporous structures such as zeolites and metal organic frameworks at temperatures T < Tc. Published experimental adsorption data for T < Tc show that the isotherms invariably display stepped characteristics. The inverse thermodynamic factor 1/Γi ≡ d ln ci/d ln fi exceeds unity for a range of fugacities fi and molar concentrations ci within the pore corresponding to the steep portion of the isotherm. With the aid of Monte Carlo simulations of isotherms for different temperatures T < Tc in a variety of zeolites (AFI, MTW, FAU, NaY, MFI and MOR), metal−organic frameworks (IRMOF-1, CuBTC, MIL-47 (V) and MIL-53 (Cr)) and covalent−organic frameworks (COF-102 and COF-108), we investigate the conditions required for 1/Γi > 1. For each of the three species investigated, data on pore concentrations ci at any given temperature below Tc fall within the binodal region for the bulk fluid phase. We present evidence to suggest that, in the concentration ranges for which 1/Γi > 1, clustering of molecules occurs. The extent of clustering is enhanced as T falls increasingly below Tc. Furthermore, molecular dynamics simulations of diffusion demonstrate that the concentration dependence of the diffusivities is markedly influenced in the regions where 1/Γi > 1. In regions where molecular clustering occurs, the Fick diffusivity shows, in some cases, a decreasing trend with concentration.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:111880
Deposited On:26 Sep 2017 12:54
Last Modified:26 Sep 2017 12:54

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