Unveiling the formation mechanism of Pb _x Pd _y intermetallic phases in solvothermal synthesis using in situ X-ray total scattering

Pd possesses attractive catalytic properties and nano-structuring is an obvious way to enhance catalytic activity. Alloying Pd with Pb has been shown to enhance the catalytic effect of alcohol oxidation. Further optimization of the catalytic effect can be accomplished by controlling the particle size and key to this is understanding the formation mechanism. By monitoring solvothermal syntheses using in situ X-ray total scattering, this study unveils the formation mechanism of Pb_xPd_y intermetallic nanoparticles. The formation occurs through a multi-step mechanism. Initially, Pd nanoparticles are formed, followed by incorporation of Pb into the Pd-structure, thus forming Pb_xPd_y intermetallic nanoparticles. By varying the reaction time and temperature, the incorporation of Pb can be controlled, thereby tailoring the phase outcome. Based on the in situ solvothermal syntheses, ex situ autoclave syntheses were performed, resulting in the synthesis of Pb₃Pd₅ and Pb₉Pd₁₃ with a purity above 93%. The catalytic effect of these intermetallic phases towards the hydrogen evolution reaction (HER) is assessed. It is found that Pd, Pb₃Pd₅, and Pb₉Pd₁₃ have comparable stabilities, however, the overpotential increases with increasing amounts of Pb.