Desulfurization of SO 2 and thiophene on surfaces and nanoparticles of molybdenum carbide: Unexpected ligand and steric effects

Ping Liu, José A. Rodriguez, James T. Muckerman

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60 Citations (Scopus)


The destruction of S-containing molecules is a very important issue in the chemical industry and the control of environmental pollution. The desulfurization of sulfur dioxide and thiophene on molybdenum carbide surfaces, α-Mo 2C(001) and δ-MoC(001), and on a Mo 8C 12 nanoparticle was studied with density functional theory. Our study reveals unexpected ligand and steric effects. The Mo 8C 12 nanoparticle behaves as actively as α-Mo 2C(001) toward SO 2 despite the high C/Mo ratio and C 2 groups. In contrast, SO 2 bonds weakly with δ-MoC(001). Spontaneous S-O bond cleavage was observed on both Mo 8C 12 and α-Mo 2C(001). Contrary to common assumptions, the C atoms are not simple spectators and play a key role in the energetics for the dissociation of SO 2. In the case of thiophene adsorption, only α-Mo 2C(001) exhibits a high chemical activity that leads to a spontaneous S-C bond cleavage. The interaction of thiophene with both δ-MoC(001) and Mo 8C 12 is weak. On the nanoparticle, steric repulsion between the C 2 groups and thiophene overcomes the high reactivity of the Mo atoms in corner or edge sites. Our results illustrate the interplay of ligand and steric effects in nanoparticles of metal compounds.

Original languageEnglish
Pages (from-to)15662-15670
Number of pages9
JournalJournal of Physical Chemistry B
Issue number40
Publication statusPublished - Oct 7 2004


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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