Although the growth mechanisms (e.g., seed-induced
growth and capping agent orientation) of bimetal nanocrystals (e.g., core–shell, alloy, segmented, and branched)
from artificial experimental speculation and theoretical calculation
have been widely accepted, precisely revealing their growth mechanisms
is still tremendously challenging. In this work, we utilized redox
reaction kinetics for the first time to successfully reveal the aqueous
sequential growth mechanism between Au and Ag nanocrystals of segmented
Ag-Au-Ag heterojunction nanorods (HJNRs) in a one-step and high-temperature
aqueous system. Herein, electrode potentials of different electrical
pairs (e.g., Ag+/Ag and AuCl4
–/Au) at 200 °C could be calculated through
using the Helgeson–Kirkham–Flowers state and other equations,
from which whether Au and Ag nanocrystals grew successively and formed
segmented Ag-Au-Ag HJNRs could be correctly assessed. The redox reaction
kinetics mechanism can also explain well the aqueous-phase growth
mechanisms of other bimetal nanocrystals and paves a promising avenue
for the design and synthesis of other one-dimensional segmented metal
nanostructures.