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The information obtained from the characterization of vanadium oxide single crystal surfaces is related to the study of vanadia nanoparticles supported on silica and alumina thin films, model systems for the so-called “supported monolayer vanadia catalysts”. It is found that these particles have properties similar to V2O3 surfaces, where the topmost V ions are involved in vanadyl groups and have a 5+ oxidation state. A vibrational spectroscopy investigation combined with DFT calculations show that the accepted interpretation of vibrational spectra from vanadia catalysts must be revised

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