Reductive and Coordinative Effects of Hydrazine in Structural Transformations of Copper Hydroxide Nanoparticles

Shape-specific copper oxide nanostructures have attracted increasing attention due to their widespread applications in energy conversion, sensing, and catalysis. Advancing our understanding of structure, composition, and surface chemistry transformations in shaped copper oxide nanomaterials during changes in copper oxidation state is instrumental from both applications and preparative nanochemistry standpoints. Here, we report the study of structural and compositional evolution of amorphous copper (II) hydroxide nanoparticles under hydrazine reduction conditions that resulted in the formation of crystalline Cu₂O and composite Cu₂O-N₂H₄ branched particles. The structure of the latter was influenced by the solvent medium. We showed that hydrazine, while being a common reducing agent in nanochemistry, can not only reduce the metal ions but also coordinate to them as a bidentate ligand and thereby integrate within the lattice of a particle. In addition to shape and composition transformation of individual particles, concurrent interparticle attachment and ensemble shape evolution were induced by depleting surface stabilization of individual nanoparticles. Not only does this study provide a facile synthetic method for several copper (I) oxide structures, it also demonstrates the complex behavior of a reducing agent with multidentate coordinating ability in nanoparticle synthesis.