Enhancing CO₂ Adsorption and Separation Properties of Aluminophosphate Zeolites by Isomorphous Heteroatom Substitutions

Mg, Co-substituted aluminophosphate zeolites with ERI framework topology (denoted as MgAPO-ERI and CoAPO-ERI) have been synthesized under hydrothermal conditions by using N,N,N′,N′-tetramethyl-1,6-hexanediamine as organic template. Their CO₂ adsorption properties are investigated in comparison to those of the pure aluminophosphate counterpart AlPO-ERI. CoAPO-ERI shows the highest CO₂ uptake of 57.3 cm³ g^–1 (273 K and 1 bar) and the highest isosteric heat of 39.0 kJ mol^–1 among the three samples. Importantly, the incorporation of Mg²⁺ and Co²⁺ ions in the framework of AlPO-ERI can greatly improve the adsorption selectivities of CO₂ over CH₄ and N₂. Whereafter, transient breakthrough simulations were investigated and further proved the advantages of heteroatoms for separations. These results demonstrate that isomorphous heteroatom substitutions in aluminophosphate zeolites play a key role in enhancing CO₂ adsorption and separation abilities.