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Influence of the Metal Oxide Substrate Structure on Vanadium Oxide Monomer Formation

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Abstract

Vanadium oxide (VOx) molecular species supported on high surface area oxide supports are active catalysts for oxidative transformations of organic molecules. Since the reactivity of VOx species depends on their molecular structure, the understanding and control of factors that determine their structure would be useful in surface molecular catalyst design. Reactive adsorption of vanadyl triisopropoxide (VOTP) to form monomeric VOx species on amorphous Al2O3 and SrTiO3 (001) surfaces has been studied by X-ray photoelectron spectroscopy (XPS). Quantitative comparison of C(1s) and V(2p3/2) peak areas has been used to determine the number of isopropoxide ligands that are replaced by V–O surface bonds. On average, three V–O surface bonds are formed during adsorption on an amorphous Al2O3 surface, as expected in the formation of a tridentate, VO4 structure, typically assigned to monomeric, surface VOx species. On the SrTiO3 (001) surface, the number of V–O surface bonds depends on the oxygen density prior to reaction with VOTP. For adsorption on the SrTiO3 surface cleaned and oxygen-annealed in ultrahigh vacuum, the number of V–O surface bonds is ca. 2. When the SrTiO3 surface has been Ar-ion sputtered prior to VOTP adsorption, the number of V–O bonds is ca. 1. This study demonstrates that the atomic structure of the support can strongly influence the molecular nature of surface VOx species.

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Acknowledgments

This material is based upon work supported by the National Science Foundation under Grant No. CHE-1058835. Brian Quezada acknowledges support from Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy (Award DE-FG02-03-ER15457).

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Authors and Affiliations

  1. Department of Chemistry, Northwestern University, Evanston, IL, 60208, USA

    Alexis M. Johnson & Peter C. Stair

  2. McCormick School of Engineering, Northwestern University, Evanston, IL, 60208, USA

    Brian R. Quezada

  3. Department of Materials Science and Engineering, Northwestern University, Evanston, IL, 60208, USA

    Laurence D. Marks

  4. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, 60439, USA

    Peter C. Stair

Authors
  1. Alexis M. Johnson
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  2. Brian R. Quezada
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Correspondence to Peter C. Stair.

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Johnson, A.M., Quezada, B.R., Marks, L.D. et al. Influence of the Metal Oxide Substrate Structure on Vanadium Oxide Monomer Formation. Top Catal 57, 177–187 (2014). https://doi.org/10.1007/s11244-013-0174-3

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