Ligand-Mediated Control of the Surface Oxidation States of Copper Nanoparticles Produced by Laser Ablation

We report on studies that demonstrate how the chemical composition of the surface of copper nanoparticles (CuNPs) - in terms of percentage copper(I/II) oxides - can be varied by the presence of N-donor ligands during their formation via laser ablation. Changing the chemical composition thus allows systematic tuning of the surface plasmon resonance (SPR) transition. The trialed ligands include pyridines, tetrazoles, and alkylated tetrazoles. CuNPs formed in the presence of pyridines, and alkylated tetrazoles exhibit a SPR transition only slightly blue shifted with respect to CuNPs formed in the absence of any ligand. On the other hand, the presence of tetrazoles results in CuNPs characterized by a significant blue shift of the order of 50-70 nm. By comparing these data also with the SPR of CuNPs formed in the presence of carboxylic acids and hydrazine, this work demonstrates that the blue shift in the SPR is due to tetrazolate anions providing a reducing environment to the nascent CuNPs, thus preventing the formation of copper(II) oxides. This conclusion is further supported by the fact that both AFM and TEM data indicate only small variations in the size of the nanoparticles, which is not enough to justify a 50-70 nm blue-shift of the SPR transition. High-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) studies further confirm the absence of Cu(II)-containing CuNPs when prepared in the presence of tetrazolate anions.