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Structural and Activity Investigation into Al3+, La3+ and Ce3+ Addition to the Phosphomolybdate Heteropolyanion for Isobutane Selective Oxidation

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Abstract

Twelve phosphomolybdate compounds were synthesized via cationic exchange and were of the form: M x H3–3x [PMo12O40] (M = Al, La or Ce; 0 ≤ x ≤ 1). These compounds were analyzed by XRD and adsorption isotherm. Aluminum addition causes a primitive cubic phase, while lanthanum and cerium yield body-centered structures. La and Ce addition reduces surface area of phosphomolybdate structure. Temperature-programmed experiments for the selective oxidation of isobutane yielded methacrolein, 3-methyl-2-oxetanone (lactone), acetic acid (not with aluminous compounds), propene (only with aluminous compounds), carbon dioxide and water. The preference for propene rather than acetic acid formation with Al3+ may be due to the smaller cation size, or primitive cubic structure. These products form via two distinct reaction processes, labeled categories 1 and 2. Category 1 formation is associated with isobutane forming products on the surface, but reaction rate determined by bulk migration of charged particles. Category 2 formation is concerned with isobutane penetrating deep within the bulk of the substrate and forming products which subsequently desorb in a series of bell-shaped humps. Methacrolein forms via both category 1 and 2, whilst all other products form via category 2 exclusively. Kinetic analysis showed apparent activation barriers for category 1 methacrolein formation range from 67 ± 2 kJ mol−1 to >350 kJ mol−1, and occur in groups with small, medium and large activation barriers. The addition of +3 metal cations to the phosphomolybdate anion increase thermal stability, significantly decreasing deactivation; IR spectroscopy shows that the Keggin structure remains intact during temperature-programmed experiments with the Al, La and Ce salts.

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Acknowledgments

Shane, Nick and Amy are appreciative of the Australian Postgraduate Award stipend. The authors are also thankful of the generous research funding supplied by the University of New England, Australia.

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Authors and Affiliations

  1. Chemistry, School of Science and Technology, University of New England, Armidale, New South Wales, Australia

    Shane M. Kendell, Amy-Sue Alston, Nick J. Ballam & Trevor C. Brown

  2. Chemistry, School of Environmental and Life Sciences, University of Newcastle, Newcastle, Australia

    Robert C. Burns

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  1. Shane M. Kendell
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  2. Amy-Sue Alston
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  3. Nick J. Ballam
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  4. Trevor C. Brown
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Correspondence to Shane M. Kendell.

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Kendell, S.M., Alston, AS., Ballam, N.J. et al. Structural and Activity Investigation into Al3+, La3+ and Ce3+ Addition to the Phosphomolybdate Heteropolyanion for Isobutane Selective Oxidation. Catal Lett 141, 374–390 (2011). https://doi.org/10.1007/s10562-010-0514-x

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