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Cation Vacant Fe3−x−y V x □ y O4 Spinel-Type Catalysts for the Oxidation of Methanol to Formaldehyde

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Abstract

The potential of Fe–V-oxide catalysts for use in methanol oxidation is explored. Our results show that although FeVO4 is active and selective for formaldehyde (FA) formation, it is not completely stable towards volatilization under reaction conditions. Attempts to stabilize Fe–V-oxide were made using titania, alumina and silica supports. However, we observe that although some stabilization is achieved using titania and alumina, the supported catalysts are sensitive to volatilization considering the relatively low content of active oxide. Compared with supported V-oxide, the results show that iron causes stabilization of vanadium decreasing its volatility. Considering the observation that the neat FeVO4 restructures to form a spinel-type phase under influence of the catalysis, we prepared a series of cation vacant spinel-type Fe3−x−y V x □ y O4 catalysts with various V/Fe ratio and consequent number of cation vacancies □. Opposed to the activity, which is rather constant irrespectively of the vanadium content, the selectivity to FA passes through a maximum of about 90% for Fe/V = 14. A spinel-type phase with the composition Fe2.62V0.19□0.20O4 was prepared and subsequently preoxidized to different degree. It is observed that the spinel-type structure is stable and that the oxidation of vanadium and iron is balanced by an increasing number of cation vacancies. Moreover, irrespectively of the original degree of preoxidation, it is found that in methanol oxidation a steady state is reached where all samples are equally active and selective and have the same composition both in the bulk and at the surface. The results clearly demonstrate that the spinel-type catalysts are phase-stable, nonvolatile and flexible in that the cations can change oxidation state retaining the same basic structure type and Fe/V ratio.

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Acknowledgments

The Swedish Research Council (VR) is acknowledged for financial support. Parts of the research were carried out at beamline I811, MAX-lab synchrotron radiation source, Lund University, Sweden. Funding for the beamline I811 project was kindly provided by The Swedish Research Council and The Knut and Alice Wallenberg Foundation.

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Authors and Affiliations

  1. Department of Chemical Engineering, Lund University, Chemical Center, P.O. Box 124, SE-221 00, Lund, Sweden

    Mariano Massa, Robert Häggblad & Arne Andersson

Authors
  1. Mariano Massa
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  2. Robert Häggblad
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  3. Arne Andersson
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Corresponding author

Correspondence to Mariano Massa.

Additional information

This work is dedicated to Professor Robert K. Grasselli on the occasion of his 80th birthday in appreciation of his contribution to oxidation catalysis on multicomponent oxides and he learning us about the active ensemble and the importance of site isolation and phase cooperation.

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Massa, M., Häggblad, R. & Andersson, A. Cation Vacant Fe3−x−y V x □ y O4 Spinel-Type Catalysts for the Oxidation of Methanol to Formaldehyde. Top Catal 54, 685–697 (2011). https://doi.org/10.1007/s11244-011-9690-1

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