Chemisorption of aromatic compounds on well-defined palladium surfaces: Studies by electron spectroscopy and electrochemistry

The chemisorption of aromatic compounds, derivatized with different functional groups, on well-defined Pd(111) surfaces was studied by a combination of Auger electron spectroscopy (AES), low energy electron diffraction (LEED), high resolution electron energy loss spectroscopy (HREELS), and electrochemistry (EC).;The results of this work led to the following trends and conclusions: (a) At low concentrations, 2,5-dihydroxythiophenol (DHT) chemisorbs on a Pd surface through both diphenolic ring and thiol group. At high concentrations, it chemisorbs only through the thiol group. (b) There is extensive intermolecular attraction between the co-adsorbed thiolated quinone and thiolated hydroquinone molecules. The interaction occurs through the Pd substrate and not through space. (c) The chemisorption properties of N-heteroaromatic compounds are pH-dependent. When the nitrogen heteroatom is protonated, it becomes very weakly surface-active. When the nitrogen heteroatom is deprotonated, surface activity stronger than the diphenolic ring is exhibited. (d) On a palladium surface, the binding strengths of ligands increase in the order: phenyl ring < quinonoid ring, < N-heteroatom < I < -SH.