Unraveling CO₂ Chemisorption in Functionalized MOFs via In Situ High-Resolution PXRD

Decarbonization strategies demand advanced CO2 capture technologies, with Metal-Organic Frameworks (MOFs) offering promising platforms. While conventional gas sorption methods provide valuable macroscopic data, optimizing CO2 adsorbents requires detailed structural and thermodynamic insights into the sorption mechanisms. We propose to expand our in situ HR-PXRD protocol, previously validated for physisorption, to investigate CO2 chemisorption in a series of MOFs capable of reacting with CO2 at low pressures, making them highly relevant for Direct Air Capture (DAC). By systematically varying CO2 pressure and temperature, we aim to extract not only fine structural details of the adsorption process but also site-specific isosteric heats of adsorption (Qst), which remain inaccessible through classical volumetric adsorption isotherms. This approach will enhance our knowledge and provide an unprecedentedly comprehensive thermodynamic and structural picture of chemisorption-based processes.