Molecular Origin of the Selectivity Differences between Palladium and Gold-Palladium in Benzyl Alcohol Oxidation: Different Oxygen Adsorption Properties

Journal Article · Wed Nov 02 00:00:00 UTC 2016 · ChemCatChem

DOI: https://doi.org/10.1002/cctc.201601295 · OSTI ID:1344268

Savara, Aditya  ^[1]; Chan-Thaw, Carine E. ^[2]; Sutton, Jonathan E.  ^[1]; Wang, Di ^[3]; Prati, Laura ^[2]; Villa, Alberto  ^[2]

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1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
2. Univ. degli Studi di Milano via Golgi, Milano (Italy). Dipartimento di Chimica
3. Karlsruhe Inst. of Technology, Eggenstein-Leopoldshafen (Germany). Inst. of Nanotechnology and Karlsruhe Nano Micro Facility

The same mechanism and microkinetic model used for benzyl alcohol oxidation over Pd/C was shown to apply to benzyl alcohol oxidation over AuPd/C. Almost all of the selectivity differences could be explained by a decrease in oxygen adsorption on AuPd. After isolating oxygen adsorption as being the origin of the selectivity differences, density functional theory was used to investigate the oxygen adsorption properties of a pure Pd surface, a pure Au surface, and an alloyed AuPd surface. Finally, the calculations showed that Au–Pd alloying decreased the oxygen adsorption properties relative to pure Pd, which explained the selectivity differences, consistent with the microkinetic modeling.

• Research Organization: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
• Sponsoring Organization: USDOE Office of Science (SC)
• Grant/Contract Number: AC05-00OR22725
• OSTI ID: 1344268
• Journal Information: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 2 Vol. 9; ISSN 1867-3880
• Publisher: ChemPubSoc EuropeCopyright Statement
• Country of Publication: United States
• Language: English