Catalytic properties of AlTM complex intermetallics: influence of the transition metal and the surface orientation on butadiene hydrogenation.
Fiche publication
Date publication
janvier 2019
Journal
Science and technology of advanced materials
Auteurs
Membres identifiés du Cancéropôle Est :
Pr GAUDRY Emilie
Tous les auteurs :
Piccolo L, Chatelier C, De Weerd MC, Morfin F, Ledieu J, Fournée V, Gille P, Gaudry E
Lien Pubmed
Résumé
Complex intermetallic compounds such as transition metal (TM) aluminides are promising alternatives to expensive Pd-based catalysts, in particular for the semi-hydrogenation of alkynes or alkadienes. Here, we compare the gas-phase butadiene hydrogenation performances of AlCo(100), -AlFe(010) and -AlRu(010) surfaces, whose bulk terminated structural models exhibit similar cluster-like arrangements. Moreover, the effect of the surface orientation is assessed through a comparison between AlCo(100) and AlCo(010). As a result, the following room-temperature activity order is determined: AlCo(100) < AlCo(010) < AlRu(010) < AlFe(010). Moreover, AlCo(010) is found to be the most active surface at 110°C, and even more selective to butene (100%) than previously investigated AlFe(010). DFT calculations show that the activity and selectivity results can be rationalized through the determination of butadiene and butene adsorption energies; in contrast, hydrogen adsorption energies do not scale with the catalytic activities. Moreover, the calculation of projected densities of states provides an insight into the AlTM surface electronic structure. Isolating the TM active centers within the Al matrix induces a narrowing of the TM d-band, which leads to the high catalytic performances of AlTM compounds.
Mots clés
106 Metallic materials, 205 Catalyst / Photocatalyst / Photosynthesis, 212 Surface and interfaces, 401 1st principle calculations, 60 New topics / Others, Al13Co4, Al13Fe4, Al13Ru4, Complex intermetallic compounds, butadiene, density functional theory, heterogeneous catalysis, hydrogenation, single-crystal surfaces
Référence
Sci Technol Adv Mater. 2019 ;20(1):557-567