Thermodynamic evidence of flexibility in H2O and CO2 absorption of transition metal ion exchanged zeolite LTA†
Abstract
Gas absorption calorimetry has been employed to probe the intercation of water and carbon dioxide with transition metal ion (TM = Mn2+, Fe2+, Co2+, Cu2+, and Zn2+) exchanged zeolite A samples. There appears to be a two-phase region, indicative of a guest-induced flexibility transition, separating hydrated zeolite A and its dehydrated form, both of which have variable water content in the single phase region. The differential enthalpy of absorption as a function of water loading directly identifies different strengths of multiple interactions along with possible binding mechanisms of Zn-A and Mn-A exhibiting the highest water absorption with most exothermic initial enthalpies of −125.28 ± 4.82 and –115.30 ± 2.56 kJ mol−1. Zn-A and Mn-A also show moderately good capture ability for CO2 with zero-coverage negative enthalpies of −55.59 ± 2.48 and −44.07 ± 1.53 kJ mol−1. The thermodynamic information derived from differential enthalpy, chemical potential and differential entropy elucidated the multistage interactive behavior of small guest molecules (H2O/CO2) and ion-exchanged frameworks.
- This article is part of the themed collection: 2018 PCCP HOT Articles