Enhancing selective CO2adsorptionvia chemical reduction of a redox-active metal–organic framework

Abstract

A new microporous framework, Zn(NDC)(DPMBI) (where NDC = 2,7-naphthalene dicarboxylate and DPMBI = N,N′-di-(4-pyridylmethyl)-1,2,4,5-benzenetetracarboxydiimide), containing the redox-active benzenetetracarboxydiimide (also known as pyromellitic diimide) ligand core has been crystallographically characterised and exhibits a BET surface area of 608.2 ± 0.7 m² g⁻¹. The crystallinity of the material is retained upon chemical reduction with sodium naphthalenide (NaNp), which generates the monoradical anion of the pyromellitic diimide ligand in the framework Zn(NDC)(DPMBI)·Na_x (where x represents the molar Na⁺/Zn²⁺ ratio of 0.109, 0.233, 0.367 and 0.378 from ICP-AES), as determined by EPR, solid state Vis-NIR spectroelectrochemistry and UV-Vis-NIR spectroscopy. The CO₂ uptake in the reduced materials relative to the neutral framework is enhanced up to a Na⁺/Zn²⁺ molar ratio of 0.367; however, beyond this concentration the surface area and CO₂ uptake decrease due to pore obstruction. The CO₂ isosteric heat of adsorption (|Q_st|) and CO₂/N₂ selectivity (S), obtained from pure gas adsorption isotherms and Ideal Adsorbed Solution Theory (IAST) calculations, are also maximised relative to the neutral framework at this concentration of the alkali metal counter-ion. The observed enhancement in the CO₂ uptake, selectivity and isoteric heat of adsorption has been attributed to stronger interactions between CO₂ and both the radical DPMBI ligand backbone and the occluded Na⁺ ions.