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

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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 languageEnglish (US)
Pages (from-to)15857-15860
Number of pages4
JournalJournal of the American Chemical Society
Volume136
Issue number45
DOIs
StatePublished - Nov 12 2014

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Oxygen vacancies
Carbon Monoxide
Mars
Oxygen
Oxidation
Molecular dynamics
Molecular Dynamics Simulation
Computer simulation
Demonstrations
Atoms
Molecules

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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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.",
author = "Lei Li and Zeng, {Xiao Cheng}",
year = "2014",
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AU - Li, Lei

AU - Zeng, Xiao Cheng

PY - 2014/11/12

Y1 - 2014/11/12

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.

AB - 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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