Abstract
Postsynthetic exchange (PSE) is a key technique for integrating sensitive linkers into metal-organic frameworks (MOFs). Despite its importance, investigations into linker distributions have primarily focused on micrometer-sized crystals due to the analytical limitations, leaving nanoparticles less explored, although they are commonly synthesized and used in applications. In particular, the emergence of core-shell nanostructures via PSE has shown potential for applications in CO2 adsorption and selective catalysis. This study addresses this gap by investigating the formation of core-shell structures on nanoparticles under diffusion-controlled PSE conditions. By analyzing volume-to-surface ratios and conducting time-dependent experiments, we confirmed that these conditions facilitate the development of core-shell architectures. We also developed a straightforward method to calculate the minimum incorporation depth using basic parameters such as particle size and the total amount of incorporated linker. The accuracy of our approach was validated against data obtained from transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy. These findings enhance the understanding of PSE in MOF nanoparticles and open up promising avenues for developing advanced MOF core-shell structures for various applications.
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