Study of carbon dioxide adsorption on a Cu-nitroprusside polymorph

A careful structural characterization was carried out to unequivocally determine the structure of the synthesized material. The TGA, DRIFTS and a Pawley fitting of the XRD powder profiles indicate that the hydrated and in situ dehydrated polymorph crystallizes in the orthorhombic space group Pnma. Meanwhile, the CO2 isosteric heat of adsorption appears to be independent of loading with an average value of 30 kJ/mol. This translates to a physisorption type interaction, where the adsorption energy corresponding to wall and lateral interactions are mutually compensated to produce, an apparently, homogeneous adsorption energy. The somewhat high adsorption energy is probably due to the confinement of the CO2 molecules in the nitroprusside pores. Statistical Physics and the Dubinin theory for pore volume filling allowed model the CO2 equilibrium adsorption process in Cu-nitroprusside. A DRIFTS test for the adsorbed CO2 displayed a peak at about 2338 cm-1 that was assigned to a contribution due to physical adsorption of the molecule. Another peak found at 2362 cm-1 evidenced that this molecule interacts with the Cu2+, which appears to act as an electron accepting Lewis acid site. The aim of the present paper is to report a Pnma stable Cu-nitroprusside polymorph obtained by the precipitation method that can adsorb carbon dioxide. -- Graphical abstract: The adsorption space of a very well characterized Cu-nitroprusside polymorph, applying carbon dioxide as probe molecule, was studied. Display Omitted Highlights: → Accurate information about the geometry of the adsorption space was provided. → Truthful data about the interactions within the adsorption space was presented. → The structure of the tested Cu-NP polymorph was established. → Was evidenced adsorbed CO2 molecules in the form of weakly bonded adducts. → Is proposed that adsorbed molecules could change the Cu-NP magnetic properties.