Density functional study of acrolein adsorption on Pt (111)

• Geometry optimization for acrolein/Pt (111) shows cis isomers are more stable than trans configurations.
• Van der Waals corrections to the energy do not change the adsorption geometries or relative adsorption energies.
• Bonding analysis indicates acrolein is adsorbed mainly by C–Pt bonds.
• The electron orbital occupation evolution indicates C pz, Pt pz and Pt dz2dz2 orbitals play important roles in the adsorption.

The electronic structure and bonding of acrolein (propenal) adsorption on Pt (111) were studied by density functional calculations (DFT). We optimized different adsorption configurations on the surface using the VASP code. The energetic study indicates that acrolein trans isomers are less stable on the Pt surface than cis configurations, which have a similar stability in all cases. We found that the inclusion of Van der Waals (vdW) corrections does not change the obtained adsorption geometries or preferential sites relative energies. We also analyzed the evolution of the chemical bonding changes in the adsorbate and the metal surface by crystal orbital overlap population (COOP) and overlap population (OP) analysis of selected bonds. Except for the η1 configuration, the adsorption of acrolein on the surface is mainly due to the formation of C–Pt bonds. We also found that the acrolein C pz orbital, perpendicular to the surface, play an important role in the adsorption, as well as Pt pz and dz2 orbitals, whose lobes are well oriented to overlap with the adsorbate orbitals.