Density functional theory study of sulfur tolerance of CO adsorption and dissociation on Rh-Ni binary metals

Kyungtae Lee, Chunshan Song, Michael J. Janik

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The effect of Ni addition to improve the sulfur tolerance of a Rh catalyst for CO dissociation was studied using density functional theory (DFT) methods. Adsorption and dissociation were considered over the (1 1 1) surfaces of binary Rh1Ni2 and Rh2Ni1 metals with comparison to pure Rh and Ni surfaces. Sulfur adsorption on the Rh 1Ni2(1 1 1) surface is 0.21 eV more endothermic than on the Rh(1 1 1) surface, suggesting that a Rh1Ni2 bimetallic catalyst has a higher sulfur tolerance than pure Rh catalysts due to a lower surface coverage of the sulfur poison. To compare catalytic activity in the presence of adsorbed sulfur, the CO dissociation rates over the binary and pure metals were calculated with 1/9 sulfur coverage. CO dissociation is fastest on the pure Rh surface under sulfur-free conditions, whereas among sulfur poisoned surfaces, the Rh1Ni2 surface shows the fastest CO dissociation rate. The CO dissociation barrier on Rh1Ni2 is destabilized less by a S coadsorbate than for the other metals. The addition of Ni atoms to a Rh catalyst improves the sulfur tolerance of the catalyst for CO dissociation by minimizing the repulsion between the adsorbed S atom and the CO dissociation transition state, as evidenced through a projected density of states analysis. The Rh1Ni2(2 2 1) stepped surface also shows a lower activation barrier and higher CO dissociation rate in the presence of sulfur than the Rh(2 2 1) stepped surface.

Original languageEnglish (US)
Pages (from-to)122-130
Number of pages9
JournalApplied Catalysis A: General
Issue number1-2
StatePublished - Dec 1 2010

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Process Chemistry and Technology


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