<sup>17</sup>O-EPR determination of the structure and dynamics of copper single-metal sites in zeolites.

Bruzzese, Paolo Cleto; Salvadori, Enrico; Jäger, Stefan; Hartmann, Martin; Civalleri, Bartolomeo; Pöppl, Andreas; Chiesa, Mario · Nat Commun · 2021

basic_science · Level V

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Abstract

The bonding of copper ions to lattice oxygens dictates the activity and selectivity of copper exchanged zeolites. By <sup>17</sup>O isotopic labelling of the zeolite framework, in conjunction with advanced EPR methodologies and DFT modelling, we determine the local structure of single site Cu<sup>II</sup> species, we quantify the covalency of the metal-framework bond and we assess how this scenario is modified by the presence of solvating H<sub>2</sub><sup>16</sup>O or H<sub>2</sub><sup>17</sup>O molecules. This enables to follow the migration of Cu<sup>II</sup> species as a function of hydration conditions, providing evidence for a reversible transfer pathway within the zeolite cage as a function of the water pressure. The results presented in this paper establish <sup>17</sup>O EPR as a versatile tool for characterizing metal-oxide interactions in open-shell systems.