Saturation properties of a supercritical gas sorbed in nanoporous materials

Abstract

The description of experimental gas adsorption data in terms of an accurate model is key to understand the adsorption mechanism and its limits. As a basic feature such a model should predict correctly the conditions under which saturation occurs. However, in the absence of bulk condensation properties for a supercritical adsorbate this matter remains open to discussions. In this study, the decreasing region of excess hydrogen adsorption isotherms measured down to 50 K is used to determine the adsorbed phase volume, density and pressure corresponding to saturation. The experimental method developed for these key measurements addresses the challenges of very low temperature adsorption measurements at high pressure. Therefore, the modifications specially made to a cryostat used in conjunction with a Sievert apparatus to reach high temperature stability (±10 mK) down to 40 K are presented. The approach is implemented on the novel nanoporous materials UMCM-1 and NOTT-112 over 50–77 K and 0–40 bar. The derived hydrogen saturation properties are found to be consistent with a Dubinin–Astakhov model. Importantly, the measured adsorbed hydrogen phase volume also compares well with the pore volume obtained from Ar porosimetry. The found saturation properties provide a physical basis to calculate consistent absolute adsorption isotherms and enthalpies, and to project the ultimate adsorption capacity of a conceptual material with a maximized specific surface area. The present findings provide additional evidence that the common view on supercritical adsorption, in which it is assumed that no liquid is formed and that the only possible mechanism involves monolayer coverage, does not hold in many nanoporous materials.