Synthesis of Silver Nanocubes in a Hydrophobic Binary Organic Solvent

Synthesis of metal nanoparticles with controlled shapes in hydrophobic solvents is challenging because homogeneous nucleation with high rate in these solvents is favorable for the formation of multiply twinned (MT) nanoparticles with spherical morphology. In this work, we report an inhomogeneous nucleation strategy in a binary hydrophobic solvent mediated by dimethyldistearylammonium chloride (DDAC), resulting in the coexistence of single-crystalline Ag polyhedrons and MT Ag quasi-spheres at the beginning of the reaction. In the consequent step, the MT Ag nanoparticles are selectively etched and dissolved through oxidation by NO3− ions (from the Ag precursor, AgNO3) with the assistance of Cl− ions (from DDAC). The dissolved Ag species are then reduced and deposited on the more stable single-crystalline polyhedrons to form Ag nanocubes. Synergy of the oxidative etching of MT particles and growth of single-crystalline particles leads to Ag nanocubes with high purity when the ripening time is long enough. For example, refluxing a mixing solvent of octyl ether and oleylamine containing AgNO3 (0.02 M) and DDAC (0.03 M) at 260 °C for 1 h results in Ag nanocubes with an average edge length of 34 nm and a purity higher than 95%.