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Mechanistic Investigation of Methanol Oxidation on Au/TiO2: A Combined DRIFT and DFT Study

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Abstract

The mechanism of methanol oxidation on a Au/TiO2 catalyst was investigated by combining in situ modulation-excitation diffuse reflectance infrared spectroscopy (MES-DRIFT) with periodic density functional theory (DFT). Adsorbed reaction intermediates and spectators were identified. Methanol dissociatively adsorbs as a methoxy (\(\mathrm{CH}_3\mathrm{O}\)) species on the titania surface, and stepwise oxidizes to formate, carboxyl and CO, carbonates and CO2 at the Au/\(\mathrm{TiO}_{2}\) interface. The role of the metal-support interface is clearly observed experimental and theoretically according to a metal–Au-assisted Mars van Krevelen mechanism. Energy barriers were calculated for each elementary step, and the methoxy oxidation was found to be the rate-limiting step in the proposed scenario.

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Acknowledgements

Financial support by CONICET and Universidad Nacional del Litoral is gratefully acknowledged. G.D.B, N.C., E.C. and P.Q. thanks PICT-2017-1342 and PICT-2019-03392 for support. S.C. acknowledges PICT-2018-01332. The authors also thank the support given by Santa Fe Science Technology and Innovation Agency (ASACTEI, Grant No. 00010-18-2014).

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  1. Instituto de Química Aplicada del Litoral (UNL-CONICET), FIQ-UNL, 3000, Santa Fe, Argentina

    G. D. Belletti, E. Colombo, N. Cabana & P. Quaino

  2. Instituto de Desarrollo Tecnológico para la Industria Química, INTEC (UNL-CONICET), 3000, Santa Fe, Argentina

    S. Collins

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  1. G. D. Belletti
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  2. E. Colombo
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  3. N. Cabana
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Correspondence to P. Quaino.

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Belletti, G.D., Colombo, E., Cabana, N. et al. Mechanistic Investigation of Methanol Oxidation on Au/TiO2: A Combined DRIFT and DFT Study. Top Catal 65, 915–925 (2022). https://doi.org/10.1007/s11244-022-01620-7

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