First-Principles Calculations of Propane Dehydrogenation over PtSn Catalysts

Density functional theory calculations have been performed to investigate the effect of Sn on the catalytic activity and selectivity of Pt catalyst in propane dehydrogenation. Five models with different Sn to Pt surface molar ratios are constructed to represent the PtSn surfaces. With the increase of the Sn content, the <i>d</i>-band of Pt is broadened, which gives rise to a downshift in the <i>d</i>-band center on the PtSn surfaces. Consequently, the bonding strength of propyl and propylene on the alloyed surfaces is lowered. With the decomposition of the adsorption energy, the change in the surface deformation energy is predicted to be the dominant factor that determines the variation in the adsorption energy on the surface alloys, while on the bulk alloys the change in the binding energy makes a major contribution. The introduction of Sn lowers the energy barrier for propylene desorption and simultaneously increases the activation energy for propylene dehydrogenation, which has a positive effect on the selectivity toward propylene production. Considering the compromise between the catalytic activity and selectivity, the Pt₃Sn bulk alloy is the best candidate for propane dehydrogenation