The nature and local environment of Au single atoms supported and stabilized on four different oxides is studied by means of DFT + U calculations using CO as probe molecule and its stretching frequency, ωe, as a fingerprint of the site where the Au atom is bound. Four oxides are considered, anatase TiO2, tetragonal ZrO2, cubic CeO2, and a perovskite LaFeO3. In this latter case a recently reported experimental study has detected a stretching mode for CO adsorbed on Au1/LaFeO3 of 2215 cm−1, with a large blue shift, ∆ω(CO) = 72 cm−1 with respect to free CO. In order to identify the Au adsorption site that can give rise to this large blue-shift we have considered five cases: (a) Au replacing a lattice cation, (Au)subM; (b) Au replacing a lattice O anion, (Au)subO; (c) Au adsorbed on the surface, (Au)ads; (d) Au bound to an extra O atom on the surface, (AuO)ads, or (e) Au bound to two extra O atoms on the surface, (AuO2)ads. It turns out that the correct reproduction of ∆ω for CO adsorbed on positively charged gold, Auδ+, is challenging for DFT. Therefore, we have performed a comparative study of Auδ+-CO molecular compounds for which ωe(CO) is known experimentally using various kinds of DFT functionals and accurate CCSD and CCSD(T) quantum chemistry methods. Also based on this comparison we propose a tentative assignment for the observed frequency of CO adsorbed on Au1/LaFeO3 single atom catalyst. Graphic Abstract: [Figure not available: see fulltext.].

Thang, H., Maleki, F., Tosoni, S., Pacchioni, G. (2021). Vibrational Properties of CO Adsorbed on Au Single Atom Catalysts on TiO2(101), ZrO2(101), CeO2(111), and LaFeO3(001) Surfaces: A DFT Study. TOPICS IN CATALYSIS [10.1007/s11244-021-01514-0].

Vibrational Properties of CO Adsorbed on Au Single Atom Catalysts on TiO2(101), ZrO2(101), CeO2(111), and LaFeO3(001) Surfaces: A DFT Study

Maleki F.;Tosoni S.;Pacchioni G.
2021

Abstract

The nature and local environment of Au single atoms supported and stabilized on four different oxides is studied by means of DFT + U calculations using CO as probe molecule and its stretching frequency, ωe, as a fingerprint of the site where the Au atom is bound. Four oxides are considered, anatase TiO2, tetragonal ZrO2, cubic CeO2, and a perovskite LaFeO3. In this latter case a recently reported experimental study has detected a stretching mode for CO adsorbed on Au1/LaFeO3 of 2215 cm−1, with a large blue shift, ∆ω(CO) = 72 cm−1 with respect to free CO. In order to identify the Au adsorption site that can give rise to this large blue-shift we have considered five cases: (a) Au replacing a lattice cation, (Au)subM; (b) Au replacing a lattice O anion, (Au)subO; (c) Au adsorbed on the surface, (Au)ads; (d) Au bound to an extra O atom on the surface, (AuO)ads, or (e) Au bound to two extra O atoms on the surface, (AuO2)ads. It turns out that the correct reproduction of ∆ω for CO adsorbed on positively charged gold, Auδ+, is challenging for DFT. Therefore, we have performed a comparative study of Auδ+-CO molecular compounds for which ωe(CO) is known experimentally using various kinds of DFT functionals and accurate CCSD and CCSD(T) quantum chemistry methods. Also based on this comparison we propose a tentative assignment for the observed frequency of CO adsorbed on Au1/LaFeO3 single atom catalyst. Graphic Abstract: [Figure not available: see fulltext.].
Articolo in rivista - Articolo scientifico
Au-CO molecular complexes; CO vibrational frequency; Density functional theory; Oxide surfaces; Single atom catalysis;
English
Thang, H., Maleki, F., Tosoni, S., Pacchioni, G. (2021). Vibrational Properties of CO Adsorbed on Au Single Atom Catalysts on TiO2(101), ZrO2(101), CeO2(111), and LaFeO3(001) Surfaces: A DFT Study. TOPICS IN CATALYSIS [10.1007/s11244-021-01514-0].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/354029
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