Influence of Metal-Ligand Coordination on the Elemental Growth and Alloying Composition of Pt-Ni Octahedral Nanoparticles for Oxygen Reduction Electrocatalysis.

Understanding the role of surfactants or ligands on the growth mechanism of metal/alloy nanoparticles (NPs) is important for controlled synthesis of functional metallic NPs with tailored structures and properties. There have been a number of works showing the significant impact of surfactants/ligands on the shape-controlled synthesis of nanocrystals with well-defined surfaces. Beyond the morphological shape control, impact of the surfactants/ligands on the alloying structure of bimetallic nanocrystals, however, still remains largely unaddressed. We reveal here a significant effect of benzoic acid ligand on the elemental growth and alloying phase structure of octahedral Pt-Ni NPs, a class of highly active electrocatalyst for oxygen reduction reaction in fuel cells. Contrary to previous reports showing the critical role of benzoic acid in directing the growth of octahedral Pt-Ni NPs, we found that benzoic acid played a minor role in forming the octahedral shape; instead, it can strongly coordinate with Ni cation and significantly slows down its reduction rate, leading to a phase separation in the Pt-Ni NP products (a mixture of Pt-rich octahedral NPs and nearly pure Ni NPs). Such phase separation further resulted in a lower catalytic activity and stability. These results help us comprehensively understand the effect of metal-ligand coordination chemistry on the elemental growth mechanism and alloying phase structure of bimetallic NPs, complementing previous emphasis on the role of surfactants in purely morphological shape control.