Coverage effects in CO dissociation on metallic cobalt nanoparticles

Bart Zijlstra, Robin Broos, Wei Chen, Heiko Oosterbeek, Ivo Filot, Emiel Hensen (Corresponding author)

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Uittreksel

The active site of CO dissociation on a cobalt nanoparticle, relevant to the Fischer-Tropsch reaction, can be computed directly using density functional theory. We investigate how the activation barrier for direct CO dissociation depends on CO coverage for step-edge and terrace cobalt sites. Whereas on terrace sites increasing coverage results in a substantial increase of the direct CO dissociation barrier, we find that this barrier is nearly independent of CO coverage for the step-edge sites on corrugated surfaces. A detailed electronic analysis shows that this difference is due to the flexibility of the adsorbed layer, minimizing Pauli repulsion during the carbon-oxygen bond dissociation reaction on the step-edge site. We constructed a simple first-principles microkinetic model that not only reproduces experimentally observed rates but also shows how migration of carbon species between step-edge and terrace sites contributes to methane formation.
TaalEngels
Pagina's7365-7372
TijdschriftACS Catalysis
Volume9
DOI's
StatusGepubliceerd - 5 jul 2019

Vingerafdruk

Carbon Monoxide
Cobalt
Nanoparticles
Carbon
Density functional theory
Methane
Chemical activation
Oxygen

Citeer dit

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title = "Coverage effects in CO dissociation on metallic cobalt nanoparticles",
abstract = "The active site of CO dissociation on a cobalt nanoparticle, relevant to the Fischer-Tropsch reaction, can be computed directly using density functional theory. We investigate how the activation barrier for direct CO dissociation depends on CO coverage for step-edge and terrace cobalt sites. Whereas on terrace sites increasing coverage results in a substantial increase of the direct CO dissociation barrier, we find that this barrier is nearly independent of CO coverage for the step-edge sites on corrugated surfaces. A detailed electronic analysis shows that this difference is due to the flexibility of the adsorbed layer, minimizing Pauli repulsion during the carbon-oxygen bond dissociation reaction on the step-edge site. We constructed a simple first-principles microkinetic model that not only reproduces experimentally observed rates but also shows how migration of carbon species between step-edge and terrace sites contributes to methane formation.",
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Coverage effects in CO dissociation on metallic cobalt nanoparticles. / Zijlstra, Bart; Broos, Robin; Chen, Wei; Oosterbeek, Heiko; Filot, Ivo; Hensen, Emiel (Corresponding author).

In: ACS Catalysis, Vol. 9, 05.07.2019, blz. 7365-7372.

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

TY - JOUR

T1 - Coverage effects in CO dissociation on metallic cobalt nanoparticles

AU - Zijlstra,Bart

AU - Broos,Robin

AU - Chen,Wei

AU - Oosterbeek,Heiko

AU - Filot,Ivo

AU - Hensen,Emiel

PY - 2019/7/5

Y1 - 2019/7/5

N2 - The active site of CO dissociation on a cobalt nanoparticle, relevant to the Fischer-Tropsch reaction, can be computed directly using density functional theory. We investigate how the activation barrier for direct CO dissociation depends on CO coverage for step-edge and terrace cobalt sites. Whereas on terrace sites increasing coverage results in a substantial increase of the direct CO dissociation barrier, we find that this barrier is nearly independent of CO coverage for the step-edge sites on corrugated surfaces. A detailed electronic analysis shows that this difference is due to the flexibility of the adsorbed layer, minimizing Pauli repulsion during the carbon-oxygen bond dissociation reaction on the step-edge site. We constructed a simple first-principles microkinetic model that not only reproduces experimentally observed rates but also shows how migration of carbon species between step-edge and terrace sites contributes to methane formation.

AB - The active site of CO dissociation on a cobalt nanoparticle, relevant to the Fischer-Tropsch reaction, can be computed directly using density functional theory. We investigate how the activation barrier for direct CO dissociation depends on CO coverage for step-edge and terrace cobalt sites. Whereas on terrace sites increasing coverage results in a substantial increase of the direct CO dissociation barrier, we find that this barrier is nearly independent of CO coverage for the step-edge sites on corrugated surfaces. A detailed electronic analysis shows that this difference is due to the flexibility of the adsorbed layer, minimizing Pauli repulsion during the carbon-oxygen bond dissociation reaction on the step-edge site. We constructed a simple first-principles microkinetic model that not only reproduces experimentally observed rates but also shows how migration of carbon species between step-edge and terrace sites contributes to methane formation.

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