Unusual Moisture-Enhanced CO₂ Capture within Microporous PCN-250 Frameworks

Developing metal–organic frameworks (MOFs) with moisture-resistant feature or moisture-enhanced adsorption is challenging for the practical CO2 capture under humid conditions. In this work, under humid conditions, the CO2 adsorption behaviors of two iron-based MOF materials, PCN-250(Fe3) and PCN-250(Fe2Co), were investigated. An interesting phenomenon is observed that the two materials demonstrate an unusual moisture-enhanced adsorption of CO2. For PCN-250 frameworks, H2O molecule induces a remarkable increase in the CO2 uptake for the dynamic CO2 capture from CO2/N2 (15:85) mixture. For PCN-250(Fe3), its CO2 adsorption capacity increases by 54.2% under the 50% RH humid condition, compared with that under dry conditions (from 1.18 to 1.82 mmol/g). Similarly, the CO2 adsorption uptake of PCN-250(Fe2Co) increases from 1.32 to 2.23 mmol/g, exhibiting a 68.9% increase. Even up to 90% RH, for PCN-250(Fe3) and PCN-250(Fe2Co), obvious increases of 43.7 and 70.2% in the CO2 adsorption capacities are observed in comparison with those under dry conditions, respectively. Molecular simulations indicate that the hydroxo functional groups (μ3-O) within the framework play a crucial role in improving CO2 uptake in the presence of water vapor. Besides, partial substitution of Fe3+ by Co2+ ions in the PCN-250 framework gives rise to a great improvement in CO2 adsorption capacity and selectivity. The excellent moisture stability (stable even after exposure to 90% RH humid air for 30 days), superior recyclability, as well as moisture-enhanced feature make PCN-250 as an excellent MOF adsorbent for CO2 capture under humid conditions. This study provides a new paradigm that PCN-250 frameworks can not only be moisture resistant but can also subtly convert the common negative effect of moisture to a positive impact on improving CO2 capture performance.