Catalysts surface poisoning by arsenic; mechanism of triphenylarsine interaction with alumina supported nickel

Yu A. Ryndin*, Jean-Pierre Candy, G. Bergeret, L. Savary, D. Uzio, J. M. Basset

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations


Hydrogenolysis of triphenylarsine (AsPh3) on alumina supported nickel (Ni/Al2O3) has been studied as model reaction for metallic catalyst poisoning. The hydrogenolysis of AsPh3 on Ni/Al2O3 occurs at temperature ranging from 303 to 443 K under 12 bars of hydrogen and in n-heptane solution. It has been followed by kinetics analysis of the AsPh3 consumption and Benzene and cylohexane evolution as well as XRD measurements of the metallic and intermetallic phase(s). At 303 K, the reaction proceeds selectively on the nickel surface, by stepwise hydrogenolysis of the As-Ph bonds, with final formation of partially decomposed Nis[AsPhx]y fragment grafted on the nickel surface. The chemical structure of the fragment (x value) does not depend on the metallic particle size, while the coverage of the nickel surface (y value) strongly decreases when the particle size of nickel increases. Increasing the temperature leads to complete hydrogenolysis of the As-Ph bonds and formation of a well characterized NiAs alloy (XRD). The mechanism of alloy formation is complex: Further hydrogenolysis of the Nis[AsPhx]y fragments leads progressively to the formation of arsenic «adatoms» which migrate quickly inside the nickel particles to form amorphous intermetallic phases (XRD) such as NiAs0.45. The reaction then proceeds slowly up to the formation of the crystalline NiAs nickeline phase (XRD). The rate of benzene hydrogenation on the various solids obtained by reaction of AsPh3 on Ni/Al2O3 was used as catalyst performance evaluation. It was found that benzene hydrogenation is already completely inhibited when the NiAs0.45 intermetallic phase is formed.

Original languageEnglish (US)
Pages (from-to)479-486
Number of pages8
JournalStudies in Surface Science and Catalysis
StatePublished - 2001
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry


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