Thermodynamics of Water–Cationic Species–Framework Guest–Host Interactions within Transition Metal Ion-Exchanged Mordenite Relevant to Selective Anaerobic Oxidation of Methane to Methanol

Low-temperature anaerobic methane conversion to methanol (MTM) using copper ion-exchanged mordenite (Cu-MOR) as the catalyst and water as the sole source of oxygen is promising for sustainable utilization of methane. Integrating in situ calorimetric, spectroscopic, and structural methodologies, we report a systematic study on energetics of water–cationic species–framework guest–host interactions as a function of water loading for several mordenites relevant to low-temperature MTM. Notably, the near-zero coverage hydration enthalpy on Cu-MOR is −133.1 ± 6.0 kJ/mol water, which is related to Cu-MOR regeneration using water as oxidant. The copper oxo sites are thermally stable up to 915 °C and remain chemically intact as an oxygen source after complete hydration and dehydration. This study underscores the importance of manipulating the oxidation state and coordination chemistry of transition metal guest species in zeolites by fine-tuning the partial pressure of water as a strategy for rational design, synthesis, and modification of catalysts.