Thermal Stability of Metal-Organic Frameworks and Encapsulation of CuO Nanocrystals for Highly Active Catalysis

We report an aerosol-based approach to study the thermal stability of metal-organic frameworks (MOFs) for gas-phase synthesis of MOF-based hybrid nanostructures used for highly active catalysis. Temperature-programmed electrospray-differential mobility analysis (TP-ES-DMA) provides the characterization of temperature-dependent morphological change directly in the gas phase, and the results are shown to be highly correlated with the structural thermal stability of MOFs determined by the traditional measurements of porosity and crystallinity. The results show that MOFs underwent thermal decomposition via simultaneous disassembly and deaggregation. Trimeric Cr-based MIL-88B-NH₂ exhibited a higher temperature of decomposition ( T_d), 350 °C, than trimeric Fe-based MIL-88B-NH₂, 250 °C. For UiO-66, a significant decrease of T_d by ≈100 °C was observed by using amine-functionalized ligands in the MOF structure. Copper oxide nanocrystals were successfully encapsulated in the UiO-66 crystal (Cu _xO@UiO-66) by using a gas-phase evaporation-induced self-assembly approach followed by a suitable thermal treatment below T_d (i.e., determined by TP-ES-DMA). Cu _xO@UiO-66 demonstrated a very high catalytic activity and stability to CO oxidation, showing at least a 3-time increase in CO conversion compared to the bare CuO nanoparticle samples. The study demonstrates a prototype methodology (1) to determine structural thermal stability of MOFs using a gas-phase electrophoretic method (TP-ES-DMA) and (2) to gas-phase synthesize CuO nanocrystals encapsulated in MOFs.