Growth of epitaxial Pt1–xPbx alloys by surface limited redox replacement and study of their adsorption properties

The surface limited redox replacement (SLRR) method has been used to design two-dimensional Pt–Pb nanoalloys with controlled thickness, composition, and structure. The electrochemical behavior of these alloys has been systematically studied as a function of alloy composition. A single-cell, two-step SLRR protocol based on the galvanic replacement of underpotentially deposited monolayers of Pb with Pt was used to grow epitaxial Pt1–xPbx (x < 0.1) alloys of up to 10 ML thickness on Au substrates. It is shown that by varying the terminating potential of the galvanic replacement step, the Pb atomic content can be controlled in the films. Electrochemical analysis of the alloys showed that the adsorption of both H and CO exhibits similar, and systematic, decreases with small increases in the Pb content. These measurements, commonly used in electrocatalysis for the determination of active surface areas of Pt, suggested area values much lower than those expected based on the net Pt composition in the alloy as measured by XPS. These results show that Pb has a strong screening effect on the adsorption of both H and CO. Moreover, changes in alloy composition result in a negative shift in the potential of the peaks of CO oxidation that scales with the increase of Pb content. The results suggest electronic and bifunctional effects of incorporated Pb on the electrochemical behavior of Pt. The study illustrates the potential of the SLRR methodology, which could be employed in the design of 2-dimensional bimetallic Pt nanoalloys for fundamental studies of electrocatalytic behavior in fuel cell reactions dependent on the nature of alloying metal and its composition