Oxygen Activation and Reaction on Pd–Au Bimetallic Surfaces

• Published in: Journal of physical chemistry. C Vol. 119; no. 21; pp. 11754 - 11762
• Main Authors: Yu, Wen-Yueh, Zhang, Liang, Mullen, Gregory M, Henkelman, Graeme, Mullins, C. Buddie
• Format: Journal Article
• Language: English
• Published: American Chemical Society 28.05.2015
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.5b02970

Pd–Au bimetallic catalysts have shown promising performance for a number of oxidative reactions. The present study utilizes reactive molecular beam scattering (RMBS), reflection–absorption infrared spectroscopy (RAIRS), temperature-programmed desorption (TPD), and density functional theory (DFT) techniques in an attempt to enhance the fundamental understanding of oxygen activation and reaction with CO on Pd–Au surfaces. Our results reveal that the presence of contiguous Pd sites is crucial for adsorption of oxygen molecules on Pd/Au(111) surfaces at 77 K. Upon heating, oxygen admolecules desorbed molecularly without detectable dissociation in O2-TPD measurements. CO-RMBS experiments indicate that at lower temperatures (77–150 K) oxygen admolecules were readily displaced by CO due to competitive adsorption. Oxygen admolecules can be thermally activated at higher temperatures (180–250 K) to react with CO to form CO2. DFT calculations show that the Pd–Au surface containing larger Pd ensembles favors dissociative CO oxidation, whereas associative CO oxidation and O2 desorption are the two main competing processes for the Pd–Au surface containing small Pd ensembles. An associative CO oxidation pathway was not experimentally observed, which is likely due to facile CO-induced O2 desorption. These results provide mechanistic insights into the interaction of oxygen with Pd–Au surfaces, which may prove informative for the rational design of Pd–Au catalysts for associated reactions involving O2 as a reactant.