Hysteretic adsorption of CO₂ onto a Cu₂(pzdc)₂(bpy) porous coordination polymer and concomitant framework distortion.

Abstract

The present study focuses on the long-range structural changes that occur in the porous coordination polymer Cu2(pzdc)2(bpy) (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4'-bipyridine), also known as CPL-2, upon adsorption of CO2 at 25 °C and up to 7 atm. The structural data were gathered using in situ diffraction studies. CPL-2 exhibited an unexpected hysteretic adsorption-desorption process. The onset of hysteresis occurs at a pressure where full occupancy of the volume of the CPL-2 galleries is achieved while the framework retains a structure similar to what is observed under ambient conditions. Moreover, the onset occurs at a CO2 partial pressure larger than 2 atm and could be related to a combination of adsorbate-adsorbent interactions and forces exerted onto the CPL-2 framework. Pore volumes estimated from fits of the Dubinin-Astakhov isotherm model against the CO2 desorption data gathered at 25 and -78.5 °C, respectively, provided further evidence of the aforementioned CPL-2 framework changes. These findings are of relevance to the understanding of adsorption processes in metal organic frameworks or coordination polymers under conditions that are of relevance to gas capture at industrial scale.