Identification of Pt-based catalysts for propane dehydrogenation via a probability analysis.

The intrinsic errors due to functionals are always a concern on the reliability of the predicted catalytic performance by density functional theory. This paper describes a probability-based computational screening study, which has successfully identified an optimal bimetallic alloy (Pt3In) for the propane dehydrogenation reaction (PDH). Considering DFT uncertainty, Pt3In was found to have an activity comparable to that of pure Pt and Pt3Sn. Meanwhile, Pt3In shows a considerable improvement in the propylene selectivity compared with pure Pt. After a complete and progressive potential energy, free energy and microkinetic analysis, Pt3In was discovered to show a great balance between activity and selectivity and reach a maximum propylene formation performance. The first dehydrogenation step was found to be the rate-controlling step on most of the facets. Apart from separating Pt atoms and covering the low coordinated step Pt atoms, the role of In can also be attributed to an apparently increasing electron transfer from In to Pt. The adsorption energies of propylene that play a key role in selectivity and activity were correlated with the d-band center, which can be used to tune a more precise PtIn ratio for the PDH reaction in the future.