Year: 2026
Type: preprint
Abstract: The creation of single-site catalysts, for which all active sites have the same structure, is a key goal in contemporary heterogeneous catalysis. Many MOF linkers present well-defined binding sites for transition metals and may thus provide access to single-site catalysts. Depending on how the metal is introduced into the linker-based binding site, however, additional undesired species such as pore-confined nanoparticles or node-bound metal centers may be formed that can be difficult to locate. Here, we introduce catalytic interrogation as a diagnostic workflow for identifying the types of active sites that contribute to the catalytic activity observed for MOF catalysts. Using a suite of MOFs with porphyrin linkers as a case study, we combine catalytic interrogation with extensive electron microscopy to shed light on the rhodium-based active sites present in the MOF. We show that for strongly coordinating binding sites that furnish leaching-proof MOF-based catalysts, post-synthetic metalation carries a significant risk of undesired nanoparticle incorporation. MOF assembly from metalated linkers, on the other hand, generates MOFs that behave as single-site catalysts.
Source: ChemRxiv
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7223146351