Molecular Probe Technique for the Assessment of the Carbon Molecular Sieve Structure

Nitrogen adsorption at 77 K is the most common technique for defining the surface area and pore volume of a porous material. However it is not adequate to assess the microporosity of carbon molecular sieves (CMS), because of activated diffusion effects. In this paper, a molecular probe technique was used to defining the pore size of CMS materials. Adsorption of gases (vapors) with different molecular sizes, were measured by a gravimetric method using a spring balance. The amount adsorbed at room temperature was recorded over a 24-h period. The following molecular probes were chosen: CO(2) (0.33 nm), C(2)H(6) (0.4 nm), n-C(4)H(10) (0.43 nm), i-C(5)H(12) (0.5 nm), and CCL(4) (0.6 nm). The micropore volumes were estimated by the Dubinin-Raduhkevich (DR) equation. Assuming that the diameters of the micropores are larger than those of the adsorbed molecules, the micropore volume distribution of each sample was estimated. The results demonstrated that the main pore size of the studied CMSs are less than 0.5 nm. One of the samples had a narrow pore size distribution in the range of 0.33-0.43 nm, which is the critical pore size for kinetic separation of oxygen from nitrogen. It is concluded that the molecular probe technique is an effective mean to assess the CMS adsorbents structure, which is not currently possible using conventional approaches with a single adsorbate, such as nitrogen or argon.