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.
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany.
Wei
W
Liu
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany.
Aditya
A
Savara
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany.
Xinguo
X
Ren
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany.
Wiebke
W
Ludwig
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany.
Karl-Heinz
KH
Dostert
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany.
Swetlana
S
Schauermann
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany.
Alexandre
A
Tkatchenko
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany.
Hans-Joachim
HJ
Freund
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany.
Matthias
M
Scheffler
density functional calculations; heterogeneous catalysis; low-temperature dehydrogenation; organic/metal interface; van der Waals interactions