Elucidating the Effect of Additives on the Growth and Stability of Cu2O Surfaces via Shape Transformation of Pre-Grown Crystals

Abstract

A new strategy of using pre-grown crystals to study preferential adsorption of various additives is demonstrated for the electrocrystallization of Cu₂O. In this method, micron-size Cu₂O crystals with well-defined cubic and octahedral shapes were first electrochemically grown, and their crystallization was resumed in a medium containing the additive to be investigated (e.g., Na⁺, NH₄⁺, SO₄^2-, Cl^-, dodecyl sulfate). This method makes it possible to systematically study the interaction of additives with specific planes (e.g., {100} of a cube and {111} of an octahedron) already present. By observing shape transformation over time, the relative stabilities of {100}, {111}, and {110} planes of Cu₂O in various growth media could be determined. During this study, a general scheme of forming new crystal shapes containing crystallographic planes that cannot be directly stabilized by preferential adsorption alone was also established (i.e., rhombicuboctahedral shape of Cu₂O containing {110} planes). This method can be extended to other crystal systems, which will enable us to classify common features of additives (e.g., charges, type of atoms) and crystallographic planes (e.g., atomic arrangement, surface termination, surface charge) required to allow for strong preferential adsorption.