The Deposition of Lead on a Pt(100) Electrode and the Effects on the Oxidation of Formic Acid

The electrodeposition of foreign metals on a platinum (Pt) electrode can be used to alter the electrochemical properties of the modified electrode. The current study employed in situ scanning tunneling microscopy (STM) to characterize the spatial structures of a monolayer and multilayer lead (Pb) electrodeposited on an ordered Pt(100) electrode in 0.1 M perchloric acid (HClO₄) with and without formic acid under potential control. The Pt(100) bead crystal used in this study was pretreated by a modified annealing and quenching method, producing a long-range ordered, unreconstructed (1 × 1) surface. The underpotential deposition (UPD) of Pb on the Pt(100) electrode resulted in a pair of sharp and reversible peak at 0.5 V (vs. Ag/AgCl), prior to the bulk deposition at E < -0.45 V in 0.1 M HClO₄ + 1 mM Pb(ClO₄)₂. Cyclic potential sweeping in the UPD regimes resulted in a stable voltammogram, but bulk Pb deposition led to varying morphologies of the profiles. Atomic resolution STM images were obtained to reveal a well-ordered Pt(100)-(√2 × √2)R45°-Pb structure and elongated rows of Pb aggregates and local (√2 × 2√2) R45° in the initial and final stages of Pb UPD, respectively. Bulk Pb deposition at E < -0.5 V led to a crystalline Pb film, but a roughened Pt(100) surface was imaged after the Pb deposit was anodically stripped. The activity of the Pt(100) electrode toward formic acid oxidation was nearly tripled after being modified with a sub-monolayer of Pb, and increased by another 20 % when it was loaded with multilayer Pb.