CO to formaldehyde transformation study on pristine and Au-modified BaTiO 3 (001) through DFT calculations.

Autor: Comparán-Padilla VE; Centro de Investigación en Química Aplicada, Química Macromolecular y Nanomateriales, Blvd. Enrique Reyna, C.P. 25294, Saltillo, Coahuila, Mexico. victor.comparan@ciqa.edu.mx., Romero-de la Cruz MT; Universidad Autónoma de Coahuila, Facultad de Ciencias Físico Matemáticas, Prol. David Berlanga S/N Edif. 'A' Unidad Camporredondo, C.P. 25000, Saltillo, Coahuila, Mexico., García-Díaz R; CONAHCYT-Universidad Autónoma de Coahuila, Facultad de Ciencias Físico Matemáticas, Prol. David Berlanga S/N Edif. 'A' Unidad Camporredondo, C.P. 25000, Saltillo, Coahuila, Mexico., Pérez-Camacho O; Centro de Investigación en Química Aplicada, Química Macromolecular y Nanomateriales, Blvd. Enrique Reyna, C.P. 25294, Saltillo, Coahuila, Mexico.
Jazyk: angličtina
Zdroj: Journal of molecular modeling [J Mol Model] 2023 Aug 23; Vol. 29 (9), pp. 285. Date of Electronic Publication: 2023 Aug 23.
DOI: 10.1007/s00894-023-05697-z
Abstrakt: Context: BaTiO 3 is one of the most important ferroelectric oxides in electronic applications. Also, it has attractive properties for catalysis that could be used for reducing contamination levels, especially carbon monoxide, CO. CO is one of the main gaseous pollutants generally released from the combustion of fossil fuel. In this work, the CO transformation on pristine and Au-modified BaTiO 3 perovskite for H 2 CO obtention is studied. The CO adsorption and hydrogenation on pristine BaTiO 3 leads to formaldehyde synthesis as the most stable product through two possible routes. Furthermore, hydrogenation stages are less probable on pristine BaTiO 3 . On Au-modified BaTiO 3 formaldehyde is the principal product too but Au adatom generates H 2 CO competition with HCOH. After BaTiO 3 modification with Au unpaired electrons were generated. These unpaired electrons are related to the adatom reactivity. According to the obtained results, pristine and Au-modified BaTiO 3 can adsorb and hydrogenate CO generating formaldehyde as the principal product. BaTiO 3 modifications with Au increase the reactivity of the perovskite in the CO hydrogenation reactions. CO hydrogenation process on Au suggests that further hydrogenation stages beyond formaldehyde are possible.
Methods: The study was performed through ab initio calculations using the periodic spin-polarized Density Functional Theory (DFT) as implemented in Quantum ESPRESSO. DFT calculations were carried out using the Plane Wave self-consistent field (PWscf). Spin density difference allows us to identify reactive regions related to dangling bonds and unpaired electrons. A plane wave basis set was used to represent the electron states. Vanderbilt pseudopotentials with nonlinear core correction were used to model the ionic cores and valence electrons interaction. Exchange-correlation energies were treated within the generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) parameterization.
(© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)
Databáze: MEDLINE
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