Chemical Deposition of Cu₂O Nanocrystals with Precise Morphology Control

Abstract

Copper(I) oxide nanoparticles (NPs) are emerging as a technologically important material, with applications ranging from antibacterial and fungicidal agents to photocatalysis. It is well established that the activity of Cu₂O NPs is dependent on their crystalline morphology. Here we describe direct preparation of Cu₂O nanocrystals (NCs) on various substrates by chemical deposition (CD), without the need of additives, achieving precise control over the NC morphology. The substrates are preactivated by gold seeding and treated with deposition solutions comprising copper sulfate, formaldehyde, NaOH, and citrate as a complexant. Production of NC deposits ranging from complete cubes to complete octahedra is demonstrated, as well as a full set of intermediate morphologies, <i>i</i>.<i>e</i>., truncated octahedra, cuboctahedra, and truncated cubes. The NC morphology is defined by the NaOH and complexant concentrations in the deposition solution, attributed to competitive adsorption of citrate and hydroxide anions on the Cu₂O {100} and {111} crystal faces and selective stabilization of these faces. A sequential deposition scheme, <i>i.e.</i>, Cu₂O deposition on pregrown Cu₂O NCs of a different morphology, is also presented. The full range of morphologies can be produced by controlling the deposition times in the two solutions, promoting the cubic and octahedral crystal habits. Growth rates in the ⟨100⟩ and ⟨111⟩ directions for the two solutions are estimated. The Cu₂O NCs are characterized by SEM, TEM, GI-XRD, and UV–vis spectroscopy. It is concluded that CD furnishes a simple, effective, generally applicable, and scalable route to the synthesis of morphologically controlled Cu₂O NCs on a variety of conductive and nonconductive surfaces