The Partial Hydrogenation of Butadiene over Al13Fe4: A Surface-Science Study of Reaction and Deactivation Mechanisms Full article
| Journal |
Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694 |
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| Output data | Year: 2015, Volume: 332, Pages: 112-118 Pages count : 7 DOI: 10.1016/j.jcat.2015.09.018 | ||||||
| Tags | Al13Fe4, Hydrogenation of butadiene, Intermetallic compounds, Non-noble metals, Surface science | ||||||
| Authors |
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| Affiliations |
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Funding (1)
| 1 | The French National Research Agency | ANR-BS10-009 |
Abstract:
Non-noble intermetallic compounds have shown promising properties as inexpensive catalyst alternatives to Pt-group metals for alkyne and alkene hydrogenation. In this work, the gas-phase hydrogenation of 1,3-butadiene over the Al13Fe4(0 1 0) surface was investigated in the 0.2–2 kPa total pressure range at 20–200 °C in a batch-type reactor coupled with an ultrahigh-vacuum setup allowing for Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). The results were compared with those previously obtained on Pd(1 0 0) in the same conditions. It is confirmed that Al–Fe is initially as active as Pd and 100% selective to butenes, including at room temperature (RT), with sequential conversions of butadiene to butenes, and butenes to butane. The main difference with Pd comes from the butenes distribution, with a cis/trans 2-butene ratio larger than unity for Al–Fe while it is near zero for Pd. The results are discussed in terms of (i) steric constraints upon π-allylic precursors to 2-butenes and (ii) involvement of adsorbed butyl intermediates allowing for hydro-isomerization of butenes competing with their hydrogenation to butane. A mechanistic reaction scheme is proposed accordingly. The sensitivity of the Al–Fe surface to oxygen-containing impurities leads to gradual deactivation under reaction conditions, which is the main issue for practical use of non-noble metal catalysts. The deactivation and oxidation processes were investigated by combining post-reaction AES measurements with several thermal/chemical treatments. Depending on the pressure conditions, the Al13Fe4 surface chemisorbs oxygen-containing species or forms an Al oxide layer. The RT activity of the surface decreases as the oxygen-containing phase coverage increases. However, this phase can be removed through high-temperature annealing.
Cite:
Piccolo L.
, Kibis L.
The Partial Hydrogenation of Butadiene over Al13Fe4: A Surface-Science Study of Reaction and Deactivation Mechanisms
Journal of Catalysis. 2015. V.332. P.112-118. DOI: 10.1016/j.jcat.2015.09.018 WOS Scopus РИНЦ ANCAN OpenAlex
The Partial Hydrogenation of Butadiene over Al13Fe4: A Surface-Science Study of Reaction and Deactivation Mechanisms
Journal of Catalysis. 2015. V.332. P.112-118. DOI: 10.1016/j.jcat.2015.09.018 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Aug 21, 2015 |
| Accepted: | Sep 28, 2015 |
| Published online: | Nov 2, 2015 |
| Published print: | Dec 1, 2015 |
Identifiers:
| Web of science: | WOS:000366073500013 |
| Scopus: | 2-s2.0-84945977322 |
| Elibrary: | 24968100 |
| Chemical Abstracts: | 2015:1744267 |
| Chemical Abstracts (print): | 163:666119 |
| OpenAlex: | W1904552494 |