CO₂ Adsorption in a Robust Iron(III) Pyrazolate‐Based MOF: Molecular‐Level Details and Frameworks Dynamics From Powder X‐ray Diffraction Adsorption Isotherms

Abstract Understanding adsorption processes at the molecular level, with multi‐technique approaches, is nowadays at the frontier of porous materials research. In this work it is shown that with a proper data treatment, in situ high‐resolution powder X‐ray diffraction (HR‐PXRD) at variable temperature and gas pressure can reveal atomic details of the accommodation sites, the framework dynamics as well as thermodynamic information (isosteric heat of adsorption) of the CO₂ adsorption process in the robust iron(III) pyrazolate‐based MOF Fe₂(BDP)₃ [H₂BDP = 1,4‐bis(1H‐pyrazol‐4‐yl)benzene]. Highly reliable “HR‐PXRD adsorption isotherms” can be constructed from occupancy values of CO₂ molecules. The “HR‐PXRD adsorption isotherms” accurately match the results of conventional static and dynamic gas sorption experiments and Monte Carlo simulations. These results are indicative of the impact of the molecular‐level behavior on the bulk properties of the system under study and of the potential of the presented multi‐technique approach to understand adsorption processes in metal–organic frameworks.