Systematic Study on the Precursor Reduction Kinetics and Growth Pattern for Size-Tunable Palladium Nanocubes

Unveiling the underlying chemistry during the growth of well-defined nanocrystals is a fundamental but challenging task in materials chemistry. Herein, Pd NCs with tunable sizes ranging from 4.5 to 23.5 nm have been synthesized in the presence of potassium acetate (KOAc). The Pd precursor variation trends of these preparation systems along with reaction time have been determined using a UV-vis spectrometer, and corresponding reduction kinetic parameters, including the apparent reduction rate constant (k) and activation energy (E_a), are calculated by regarding the reduction processes as quasi-first-order reactions. It is confirmed that the introduction of KOAc does not affect the value of the E_a of different reaction systems. The interrelationship of k, product size (d), and reaction temperature (T) is discussed in depth. Results indicate that the three parameters are closely related, and for given reaction systems, they are specified. With the careful investigation of six specific systems (reaction systems with 10 mM, 20 mM KOAc at 55 °C, with 5 mM, 10 mM KOAc at 65 °C, without KOAc at 75 °C, and with 5 mM KOAc at 85 °C), the growth pattern of Pd NCs is described with an empirical expression and is further confirmed as a synergistic result of k and T.