Adsorption and decomposition of cyclohexanone (C₆H ₁₀O) on Pt(111) and the (2 × 2) and (√3 × √3)R30°-Sn/Pt(111) surface alloys

Adsorption and decomposition of cyclohexanone (C₆H ₁₀O) on Pt(111) and on two ordered Pt-Sn surface alloys, (2 × 2)-Sn/Pt(111) and (√3 × √3)R30°-Sn/Pt(111), formed by vapor deposition of Sn on the Pt(111) single crystal surface were studied with TPD, HREELS, AES, LEED, and DFT calculations with vibrational analyses. Saturation coverage of C₆H₁₀O was found to be 0.25 ML, independent of the Sn surface concentration. The Pt(111) surface was reactive toward cyclohexanone, with the adsorption in the monolayer being about 70% irreversible. C₆H₁₀O decomposed to yield CO, H ₂O, H₂, and CH₄. Some C-O bond breaking occurred, yielding H₂O and leaving some carbon on the surface after TPD. HREELS data showed that cyclohexanone decomposition in the monolayer began by 200 K. Intermediates from cyclohexanone decomposition were also relatively unstable on Pt(111), since coadsorbed CO and H were formed below 250 K. Surface Sn allowed for some cyclohexanone to adsorb reversibly. C₆H ₁₀O dissociated on the (2 × 2) surface to form CO and H ₂O at low coverages, and methane and H₂ in smaller amounts than on Pt(111). Adsorption of cyclohexanone on (√3 × √3)R30°-Sn/Pt(111) at 90 K was mostly reversible. DFT calculations suggest that C₆H₁₀O adsorbs on Pt(111) in two configurations: by bonding weakly through oxygen to an atop Pt site and more strongly through simultaneously oxygen and carbon of the carbonyl to a bridged Pt-Pt site. In contrast, on alloy surfaces, C₆H₁₀O bonds preferentially to Sn. The presence of Sn, furthermore, is predicted to make the formation of the strongly bound C₆H₁₀O species bonding through O and C, which is a likely decomposition precursor, thermodynamically unfavorable. Alloying with Sn, thus, is shown to moderate adsorptive and reactive activity of Pt(111).