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The early stages of Pt electrodeposition (0.615-0.620 V vs RHE) on highly oriented pyrolytic graphite (HOPG) from chloroplatinic acid at 25 o C have been studied by ex-situ STM and SEM imaging complemented with electrochemical data. Nucleation and 3D growth of Pt initiate at HOPG surface defects. Large Pt agglomerates containing flat crystallites with well-defined geometries are found around HOPG steps. Pt crystallites formed by 1-2 nm size clusters become more compact as the electrodeposition potential is shifted negatively or the Pt electrodeposited charge is increased. High-resolution STM imaging reveals large uncovered HOPG areas with the nearest-neighbor C-C distance d=0.24±0.02 nm and flat hexagonal Pt crystallites

Early stages of platinum electrodeposition on highly oriented pyrolytic graphite: scanning tunneling microscopy imaging and reaction pathway