CO PROX over Pt–Sn/Al2O3: A combined kinetic and in situ DRIFTS study

• CO PROX was studied over Pt/Al2O3 and Pt–Sn/Al2O3 with a well-defined particle size.
• Two distinct kinetics were measured over both samples.
• DRIFTS analysis showed segregation of Pt–Sn after introduction of O2.
• A bifunctional mechanism is proposed with CO adsorbed on Pt and oxygen on SnOx sites.

Preferential oxidation of CO (PROX) in hydrogen-rich mixtures was studied over alumina-supported Pt and Pt–Sn catalysts, which exhibited a well-defined metal particle size. The reaction rate was much faster over Pt–Sn/Al2O3 than over Pt/Al2O3. Significantly different apparent activation energies and oxygen reaction orders were found for both samples. Whereas the CO PROX kinetics over Pt/Al2O3 could be described by oxygen adsorption as being rate-determining step, this was not the case for Pt–Sn. In situ Diffuse Reflectance Infrared Fourier Transformed Spectroscopy (DRIFTS) showed that Pt–Sn, initially under a mixture of 1% CO/80% H2, segregated upon the introduction of 2% O2, even at temperatures where the alloy was stable under reducing conditions. For the CO PROX reaction over Pt–Sn/Al2O3 a bifunctional mechanism is proposed with CO and H being adsorbed on the platinum sites and oxygen being channeled from neighboring SnOx sites. This work suggests a Mars–Van Krevelen type of mechanism for the SnOx site, in agreement with the low value of 0.2 for the oxygen reaction order over Pt–Sn.

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