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Characterization of Iron Species in Ex-Framework FeZSM-5 by Electrochemical Methods

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Abstract

Solid state electrochemistry is described as a method to characterize iron species in the different stages of the preparation of ex-framework FeZSM-5. The ex-framework method comprises the hydrothermal synthesis of isomorphously substituted FeZSM-5, followed by calcination at 823 K and steam treatment (300 mbar H2O in N2) at 873 K. Incorporation of FeZSM-5 samples in graphite-polyester composite (GPC) electrodes and identification of the electrochemical response provides information on the structural environment and oxidation state of electroactive iron species in the zeolite. 57Fe Mössbauer spectroscopy and TEM analysis were additionally used to interpret the electrochemical responses. Tetrahedral iron atoms in framework positions were the only species observed in the as-synthesized material. After calcination, also isolated extra-framework iron ions and oligonuclear iron--oxo complexes were identified, as well as a minor amount of FeOx nano-particles. The steaming procedure leads to extensive formation of the FeOx nano-particles of 1-2 nm in size, which were also identified by TEM. Both oxidative as well as reductive dissolution processes have been observed for the nano-particles, suggesting the presence of both Fe(II) and Fe(III) oxidation states in the steamed FeZSM-5, which is confirmed by Mössbauer spectroscopy. Tetrahedrally coordinated iron atoms in framework positions, as well as the isolated extra-framework iron ions and oligonuclear iron-oxo complexes in octahedral positions, yield electron-transfer processes that approach that of strongly electrode-attached species with distinctive variations of the electrochemical parameters on the pH and the potential scan rate.

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Authors and Affiliations

  1. Department of Analytical Chemistry, University of Valencia, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain

    A. Doménech

  2. Industrial Catalysis, DelftChemTech, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands

    J. Pérez-Ramirez, A. Ribera, F. Kapteijn, G. Mul & J.A. Moulijn

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  1. A. Doménech
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Doménech, A., Pérez-Ramirez, J., Ribera, A. et al. Characterization of Iron Species in Ex-Framework FeZSM-5 by Electrochemical Methods. Catalysis Letters 78, 303–312 (2002). https://doi.org/10.1023/A:1014937424671

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