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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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.
Originele taal-2Engels
Pagina's (van-tot)7365-7372
Aantal pagina's8
TijdschriftACS Catalysis
Volume9
Nummer van het tijdschrift8
DOI's
StatusGepubliceerd - 2 aug 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, Nr. 8, 02.08.2019, 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 - 2019/8/2

Y1 - 2019/8/2

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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.

KW - DFT

KW - Fischer-Tropsch synthesis

KW - activation energy

KW - lateral interactions

KW - microkinetic modeling

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U2 - 10.1021/acscatal.9b01967

DO - 10.1021/acscatal.9b01967

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SP - 7365

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