Nature and Topology of Metal–Oxygen Binding Sites in Zeolite Materials: 17O High-Resolution EPR Spectroscopy of Metal-Loaded ZSM-5

Determining structural models is pivotal to the rational understanding and development of heterogeneous catalytic systems. A paradigmatic case is represented by open‐shell metals supported on oxides, where the catalytic properties crucially depend on the nature of the metal–oxygen bonds and the extent of charge and spin transfer. Through a combination of selective 17O isotopic enrichment and the unique properties of open‐shell s‐state monovalent Group 12 cations, we derive a site‐specific topological description of active sites in an MFI zeolite. We show that just a few selected sites out of all possible are populated and that the relative occupancies depend on the specific properties of the metal, and we provide maps of charge and spin transfer at the metal–oxygen interface. This approach is not restricted to zeotype materials, rather it is applicable to any catalysts supported on oxygen‐containing materials.