Direct simulation evidence of generation of oxygen vacancies at the golden cage au16 and TiO2 (110) interface for co oxidation

Lei Li; Xiao Cheng Zeng

doi:10.1021/ja508666a

Direct simulation evidence of generation of oxygen vacancies at the golden cage au₁₆ and TiO₂ (110) interface for co oxidation

Lei Li, Xiao Cheng Zeng^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

54 Citations (Scopus)

Abstract

We show Born-Oppenheimer molecular dynamics (BOMD) simulation evidence of the generation of oxygen vacancies at the golden cage Au₁₆ and TiO₂ (110) interface for CO oxidation. Unlike the conventional Langmuir-Hinshelwood (L-H) mechanism, the CO molecule adsorbed at the perimeter Au sites of Au₁₆ tends to attack a nearby lattice oxygen atom on the TiO₂ (110) surface rather than the neighboring co-adsorbed molecular O₂. Our large-scale BOMD simulation provides, to our knowledge, the first real-time demonstration of feasibility of the Mars-van Krevelen (M-vK) mechanism as evidenced by the generation of oxygen vacancies on the TiO₂ surface in the course of the CO oxidation. Furthermore, a comparative study of the CO oxidation at the golden cage Au₁₈ and TiO₂ interface suggests that the L-H mechanism is more favorable than the M-vK mechanism due to higher structural robustness of the Au₁₈ cage. It appears that the selection of either M-vK or L-H mechanism for the CO oxidation is dependent on the structural fluxionality of the Au cage clusters on the TiO₂ support.

Original language	English
Pages (from-to)	15857-15860
Journal	Journal of the American Chemical Society
Volume	136
Issue number	45
DOIs	https://doi.org/10.1021/ja508666a
Publication status	Published - 12 Nov 2014
Externally published	Yes

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title = "Direct simulation evidence of generation of oxygen vacancies at the golden cage au16 and TiO2 (110) interface for co oxidation",

abstract = "We show Born-Oppenheimer molecular dynamics (BOMD) simulation evidence of the generation of oxygen vacancies at the golden cage Au16 and TiO2 (110) interface for CO oxidation. Unlike the conventional Langmuir-Hinshelwood (L-H) mechanism, the CO molecule adsorbed at the perimeter Au sites of Au16 tends to attack a nearby lattice oxygen atom on the TiO2 (110) surface rather than the neighboring co-adsorbed molecular O2. Our large-scale BOMD simulation provides, to our knowledge, the first real-time demonstration of feasibility of the Mars-van Krevelen (M-vK) mechanism as evidenced by the generation of oxygen vacancies on the TiO2 surface in the course of the CO oxidation. Furthermore, a comparative study of the CO oxidation at the golden cage Au18 and TiO2 interface suggests that the L-H mechanism is more favorable than the M-vK mechanism due to higher structural robustness of the Au18 cage. It appears that the selection of either M-vK or L-H mechanism for the CO oxidation is dependent on the structural fluxionality of the Au cage clusters on the TiO2 support.",

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N2 - We show Born-Oppenheimer molecular dynamics (BOMD) simulation evidence of the generation of oxygen vacancies at the golden cage Au16 and TiO2 (110) interface for CO oxidation. Unlike the conventional Langmuir-Hinshelwood (L-H) mechanism, the CO molecule adsorbed at the perimeter Au sites of Au16 tends to attack a nearby lattice oxygen atom on the TiO2 (110) surface rather than the neighboring co-adsorbed molecular O2. Our large-scale BOMD simulation provides, to our knowledge, the first real-time demonstration of feasibility of the Mars-van Krevelen (M-vK) mechanism as evidenced by the generation of oxygen vacancies on the TiO2 surface in the course of the CO oxidation. Furthermore, a comparative study of the CO oxidation at the golden cage Au18 and TiO2 interface suggests that the L-H mechanism is more favorable than the M-vK mechanism due to higher structural robustness of the Au18 cage. It appears that the selection of either M-vK or L-H mechanism for the CO oxidation is dependent on the structural fluxionality of the Au cage clusters on the TiO2 support.

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