Toward Low-Temperature Dehydrogenation Catalysis: Isophorone Adsorbed on Pd(111)

Adsorbate geometry and reaction dynamics play essential roles in catalytic processes at surfaces. Here we present a theoretical and experimental study for a model functional organic/metal interface: isophorone (C₉H₁₄O) adsorbed on the Pd(111) surface. Density functional theory calculations with the Perdew–Burke–Ernzerhoff (PBE) functional including van der Waals (vdW) interactions, in combination with infrared spectroscopy and temperature-programmed desorption (TPD) experiments, reveal the reaction pathway between the weakly chemisorbed reactant (C₉H₁₄O) and the strongly chemisorbed product (C₉H₁₀O), which occurs by the cleavage of four C–H bonds below 250 K. Analysis of the TPD spectrum is consistent with the relatively small magnitude of the activation barrier derived from PBE+vdW calculations, demonstrating the feasibility of low-temperature dehydrogenation