Halogen-induced corrosion of platinum.

The interaction of Cl with Pt(110) was studied in UHV by scanning tunneling microscopy, low-energy electron diffraction, temperature-programmed desorption, and DFT calculations. Up to half a monolayer (ML) of Cl forms an adsorbate structure. Compression to higher local coverages leads to erosion of Pt atoms from the top layer and formation of PtCl(4) pentamers. Annealing results in healing of the Pt defects and formation of a long-range-ordered PtCl(4)/Cl/Pt(110) adlayer that is remarkably similar to the adlayer structure found after deposition of [PtCl(4)](2-) from an electrolyte onto Au(100). Coadsorption of 0.5 ML of Cl with CO initiates PtCl(4) formation, but no volatile compounds are formed under these conditions. In similar experiments with Br, the original Pt surface is left intact, even if Br is compressed to local coverages of 0.75 ML, in agreement with the expected lower corrosion activity of Br.