Catalytic properties of Al13TM4 complex intermetallics: influence of the transition metal and the surface orientation on butadiene hydrogenation. Issue 1 (31st December 2019)

• Record Type: Journal Article
• Authors: Piccolo, Laurent; Chatelier, Corentin; De Weerd, Marie-Cécile; Morfin, Franck; Ledieu, Julian; Fournée, Vincent; Gille, Peter; Gaudry, Emilie
• Is Part Of: Science and technology of advanced materials. Volume 20:Issue 1(2019)
• Page Start: 557
• Page End: 567
• Publication Date: 2019-12-31
• Subjects: Complex intermetallic compounds -- Al13Fe4 -- Al13Co4 -- Al13Ru4 -- heterogeneous catalysis -- hydrogenation -- butadiene -- density functional theory -- single-crystal surfaces; 60 New topics / Others -- 106 Metallic materials -- 205 Catalyst / Photocatalyst / Photosynthesis -- 212 Surface and interfaces -- 401 1st principle calculations; Materials -- Technological innovations -- Periodicals; 620.112
• DOI: 10.1080/14686996.2019.1608792
• Languages: English
• ISSNs: 1468-6996

Abstract

ABSTRACT: 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 o- Al13 Co4 (100), m -Al13 Fe4 (010) and m -Al13 Ru4 (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 o- Al13 Co4 (100) and o- Al13 Co4 (010). As a result, the following room-temperature activity order is determined: Al13 Co4 (100) < Al13 Co4 (010) < Al13 Ru4 (010) < Al13 Fe4 (010). Moreover, Al13 Co4 (010) is found to be the most active surface at 110°C, and even more selective to butene (100%) than previously investigated Al13 Fe4 (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 Al13 TM4 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 Al13 TM4 compounds. Graphical abstract: uf0001