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Theoretical Study of the Water–Gas Shift Reaction on a Au/Hematite Model Catalyst

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Abstract

Using the density functional theory, the mechanism of the water–gas shift reaction has been investigated employing a model catalyst formed by a Au5 cluster supported on the Fe-terminated (0001) face of hematite (α-Fe2O3), to better understand the role played by the metal–oxide interface in this reaction. Our results indicate that the Au5/hematite model catalyst has a good performance to catalyze the reaction following the so-called adsorptive mechanism. The presence of Au favors the development of the reaction due mainly to the following factors: (i) H2O dissociates very easily at the metal–oxide interface producing OH species; (ii) CO adsorbs strongly on a Au site nearby the position of OH; (iii) the hydroxycarbonyl intermediate (HOCO) is formed at the interface from CO and OH with a low activation barrier; and (iv) after hydrogen releasing, CO2 is desorbed with relative facility from the interface region. The formation of H2 is the stage of the whole reaction that more energy demands; however, this process is favored if one hydrogen atom comes directly from HOCO, instead of from two hydrogen atoms bound to surface oxygen anions.

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Acknowledgements

Authors thank Universidad Nacional del Sur (UNS), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), and Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT) of Argentina for financial support.

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Authors and Affiliations

  1. IFISUR, Universidad Nacional del Sur (UNS-CONICET), Av. Alem 1253, 8000, Bahía Blanca, Argentina

    Silvia A. Fuente & Patricia G. Belelli

  2. INQUISUR, Departamento de Química, Universidad Nacional del Sur (UNS)-CONICET, Av. Alem 1253, 8000, Bahía Blanca, Argentina

    Carolina Zubieta & Ricardo M. Ferullo

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  1. Silvia A. Fuente
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  2. Carolina Zubieta
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Correspondence to Silvia A. Fuente.

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Fuente, S.A., Zubieta, C., Ferullo, R.M. et al. Theoretical Study of the Water–Gas Shift Reaction on a Au/Hematite Model Catalyst. Top Catal 62, 908–917 (2019). https://doi.org/10.1007/s11244-019-01174-1

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