Jump to main content
Jump to site search

Issue 20, 2003
Previous Article Next Article

Redox behaviour of over-exchanged Fe/ZSM5 zeolites studied with in-situ soft X-ray absorption spectroscopy

Author affiliations


The oxidation and reduction behaviour of calcined over-exchanged Fe/ZSM5 has been studied using soft X-ray absorption by measuring the average iron valence under (2 mbar) helium, oxygen and deNOx (HC-SCR) conditions between room temperature and 350 °C. The results (probing depth of approximately 4 nm) show that Fe/ZSM5 is an extremely flexible redox system. The calcination procedure (severe calcination: heating rate 5 °C min−1, as normally used in the literature; mild calcination: heating rate 0.5 °C min−1) is proven to be important to optimise the reducibility of iron. Upon mild calcination Fe/ZSM5 has an average valence of 2.9 under oxygen (5% in helium), of 2.5 under pure helium at room temperature (RT), and of 2.1 under pure helium at 350 °C. Upon severe calcination Fe/ZSM5 shows higher average valences, in agreement with the assumption that part of the iron in this sample is positioned in small iron-oxide nanoparticles at the outer surface of the zeolite crystals. During heating in helium, the valence reaches a minimum value before slightly rising again (re-oxidation) when the temperature is kept constant. It is also found that the X-ray irradiation is able to affect the average valence by values up to 0.10. This study confirms that iron in ‘over-exchanged’ Fe/ZSM5 consists dominantly of highly reactive iron complexes, where the iron is (distorted) octahedral FeIII in the oxidised state. The implications for the reaction mechanism for the N2O decomposition and the nature of the α-oxygen sites are discussed, in relation to recent developments in the understanding of iron non-heme enzymes.

Back to tab navigation

Article information

30 May 2003
26 Aug 2003
First published
09 Sep 2003

Phys. Chem. Chem. Phys., 2003,5, 4484-4491
Article type

Redox behaviour of over-exchanged Fe/ZSM5 zeolites studied with in-situ soft X-ray absorption spectroscopy

W. M. Heijboer, A. A. Battiston, A. Knop-Gericke, M. Hävecker, H. Bluhm, B. M. Weckhuysen, D. C. Koningsberger and F. M. F. de Groot, Phys. Chem. Chem. Phys., 2003, 5, 4484
DOI: 10.1039/B306130M

Social activity

Search articles by author