Quantitative Analysis of the Multiple Roles Played by Halide Ions in Controlling the Growth Patterns of Palladium Nanocrystals

Abstract Despite the pivotal roles played by halide ions (e. g., Cl − and Br − ) in directing the evolution of seeds into metal nanocrystals with diverse shapes, it is still unclear how halides affect the reduction kinetics of a salt precursor and thus the outcome of a synthesis. Here we report a quantitative analysis of the multiple roles played by halides in controlling the growth behaviors of Pd seeds with cubic and octahedral shapes, respectively. Our quantitative measurements clearly indicate the existence of a transition point around 10 −3 mM min −1 for the reduction rate, which separates the reduction into two distinctive pathways (solution versus surface) for the formation of completely different products. More significantly, we demonstrate that the speciation, reduction kinetics, and reduction pathway of a Pd(II) precursor can all be manipulated by varying the type and/or amount of halides introduced into a synthesis for the deterministic formation of a specific product. This work represents a critical step forward in achieving a quantitative understanding of the multiple roles of halides involved in the shape‐controlled synthesis of Pd nanocrystals, with the knowledge potentially extendible to other noble metals and their alloys.