Issue 15, 2021

Framework coordination of single-ion Cu2+ sites in hydrated 17O-ZSM-5 zeolite

Abstract

Single metal ion sites supported on zeolites are an interesting topic both in basic research and in applied, heterogeneous catalysis. Of particular interest is the interfacial coordination chemistry of the metal i.e. the formation of the inner-sphere coordination complex with framework atoms and/or coordinating molecules. In this work, we explore the interfacial coordination chemistry of single-ion Cu2+ sites, assessing the nature of the Cu–O bond with coordinating oxygen donor atoms of the framework and water molecules. Isolated Cu2+ species are prepared in ZSM-5 through oxidation of the corresponding Cu+ species, introduced via gas phase reaction, and then hydrated. Pulsed ENDOR and HYSCORE spectroscopies together with selective 17O isotopic labelling of the oxide ions, either as framework oxygen or belonging to solvating water, are applied in situ to gain an atomistic structural description of the paramagnetic species formed at the interface and an insight into the properties of the Cu–O bonds. We prove that single-ion Cu2+ sites adopt a square planar coordination geometry, maintain a strong interaction with the zeolite framework even in presence of solvating water molecules and that the Cu–O bond has a non-negligible covalent character. Further, we compare the hyperfine data obtained for Cu2+17O with VO2+17O and Zn+17O and rationalise the observed trends within the framework of ligand field theory providing useful criteria for the interpretation of hyperfine data. The level of detail afforded by 17O labelling and EPR techniques is remarkable in the understanding of the interfacial coordination chemistry of single-ion sites stabilised by zeolites.

Graphical abstract: Framework coordination of single-ion Cu2+ sites in hydrated 17O-ZSM-5 zeolite

Supplementary files

Article information

Article type
Paper
Submitted
11 may 2021
Accepted
02 iyl 2021
First published
02 iyl 2021

Catal. Sci. Technol., 2021,11, 5191-5199

Framework coordination of single-ion Cu2+ sites in hydrated 17O-ZSM-5 zeolite

A. Actis, E. Salvadori and M. Chiesa, Catal. Sci. Technol., 2021, 11, 5191 DOI: 10.1039/D1CY00838B

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