Evolution of steady-state material properties during catalysis: Oxidative coupling of methanol over nanoporous Ag0.03Au0.97

• Published in: Journal of catalysis 2019-10, Vol.380 (C)
• Main Authors: Zugic, Branko, van Spronsen, Matthijs A., Heine, Christian, Montemore, Matthew M., Li, Yuanyuan, Zakharov, Dmitri N., Karakalos, Stavros, Lechner, Barbara A. J., Crumlin, Ethan, Biener, Monika M., Frenkel, Anatoly I., Biener, Juergen, Stach, Eric A., Salmeron, Miquel B., Kaxiras, Efthimios, Madix, Robert J., Friend, Cynthia M.
• Format: Article
• Language: English
• Subjects: Diluted alloys; In situ/operando multimodal approach; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Metastability; Nanoporous Au; Selective oxidation of CH3OH
• ISSN: 0021-9517; 1090-2694

Activating pretreatments are used to tune surface composition and structure of bimetallic-alloy catalysts. Herein, the activation-induced changes in material properties of a nanoporous Ag0.03Au0.97 alloy and their subsequent evolution under steady-state CH3OH oxidation conditions are investigated. Activation using O3 results in AgO and Au2O3, strongly enriching the near-surface region in Ag. These oxides reduce in the O2/CH3OH mixture, yielding CO2 and producing a highly Ag-enriched surface alloy. At the reaction tem-perature (423 K), Ag realloys gradually with Au but remains enriched (stabilized by surface O) in the top few nanometers, producing methyl formate selectively without significant deactivation. At higher tem-peratures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These find-ings demonstrate that material properties determining catalytic activity are dynamic and that metastable (kinetically trapped) forms of the material may be responsible for catalysis, providing guiding principles concerning the activation of heterogeneous catalysts for selective oxidation.