Theoretical and Experimental Evaluation of the Reduction Potential of Straight-Chain Alcohols for the Designed Synthesis of Bimetallic Nanostructures.

Recently, the development of bimetallic nanoparticles with functional properties has been attempted extensively but with limited control over their morphological and structural properties. The reason was the inability to control the kinetics of the reduction reaction in most liquid-phase syntheses. However, the alcohol reduction technique has demonstrated the possibility of controlling the reduction reaction and facilitating the incorporation of other phenomena such as diffusion, etching, and galvanic replacement during nanostructure synthesis. In this study, the reduction potential of straight-chain alcohols has been investigated using molecular orbital calculations and experimentally verified by reducing transition metals. The alcohols with a longer chain exhibited higher reduction potential, and 1-octanol was found to be the strongest among alcohols considered. Furthermore, the experimental evaluation carried out via the synthesis of metallic Cu, Ni, and Co particles was consistent with the theoretical predictions. The reaction mechanism of metallic particle formation was also studied in detail in the Ni-1-octanol system, and the metal ions were confirmed to be reduced via the formation of nickel alkoxide. The results of this investigation were successfully implemented to synthesize Cu-Ni bimetallic nanostructures (core-shell, wire, and tube) via the incorporation of diffusion and etching besides the reduction reaction. These results suggest that the designed synthesis of a wide range of bimetallic nanostructures with more refined control has become possible.