Mechanistic Study of 1,3-Butadiene Formation in Acetylene Hydrogenation over the Pd-Based Catalysts Using Density Functional Calculations

Bo Yang, Robbie Burch, Christopher Hardacre*, P. Hu, Philip Hughes

*Corresponding author for this work

Research output: Contribution to journalArticle

44 Citations (Scopus)
625 Downloads (Pure)

Abstract

Green oil, which leads to the deactivation of the catalysts used for the selective hydrogenation of acetylene, has long been observed but its formation mechanism is not fully understood. In this work, the formation of 1,3-butadiene, known to be the precursor of green oil, on both Pd(111) and Pd(211) surfaces is examined using density functional theory calculations. The pathways containing C-2 + C-2 coupling reactions as well as the corresponding hydrogenation reactions are studied in detail. Three pathways for 1,3-butadiene production, namely coupling plus hydrogenation and further hydrogenation, hydrogenation plus coupling plus hydrogenation, and a two step hydrogenation followed by coupling, are determined. By comparing the effective barriers, we identify the favored pathway on both surfaces. A general understanding toward the deactivation process of the industrial catalysts is also provided. In addition, the effects of the formation of subsurface carbon atoms as well as the Ag alloying on the 1,3-butadiene formation on Pd-based catalysts are also investigated and compared with experimental results.

Original languageEnglish
Pages (from-to)1560-1567
Number of pages8
JournalThe Journal of Physical Chemistry C
Volume118
Issue number3
Early online date31 Dec 2013
DOIs
Publication statusPublished - 23 Jan 2014

Keywords

  • GALLIUM INTERMETALLIC COMPOUNDS
  • INITIO MOLECULAR-DYNAMICS
  • TOTAL-ENERGY CALCULATIONS
  • AUGMENTED-WAVE METHOD
  • ETHENE-RICH STREAMS
  • SELECTIVE HYDROGENATION
  • PALLADIUM CATALYSTS
  • DEACTIVATION BEHAVIOR
  • CARBON-MONOXIDE
  • BASIS-SET

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Projects

R1967CHM: Castech <CHEM/MATHS>

Goguet, A., Hardacre, C., Hu, P., James, S., Kohanoff, J., Lagunas-Castedo, C., Marr, A., Paxton, A., Rooney, D., Shekhtman, S., Sheldrake, G. & Thompson, J.

01/08/200831/12/2014

Project: Research

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