Ethylene Epoxidation at the Phase Transition of Copper Oxides.

Autor: Greiner MT; Fritz-Haber-Institut, Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany., Jones TE; Fritz-Haber-Institut, Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany., Klyushin A; Fritz-Haber-Institut, Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany., Knop-Gericke A; Fritz-Haber-Institut, Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany., Schlögl R; Fritz-Haber-Institut, Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2017 Aug 30; Vol. 139 (34), pp. 11825-11832. Date of Electronic Publication: 2017 Aug 15.
DOI: 10.1021/jacs.7b05004
Abstrakt: Catalytic materials tend to be metastable. When a material becomes metastable close to a thermodynamic phase transition it can exhibit unique catalytic behavior. Using in situ photoemission spectroscopy and online product analysis, we have found that close to the Cu 2 O-CuO phase transition there is a boost in activity for a kinetically driven reaction, ethylene epoxidation, giving rise to a 20-fold selectivity enhancement relative to the selectivity observed far from the phase transition. By tuning conditions toward low oxygen chemical potential, this metastable state and the resulting enhanced selectivity can be sustained. Using density functional theory, we find that metastable O precursors to the CuO phase can account for the selectivity enhancements near the phase transition.
Databáze: MEDLINE