A Non-Autonomous Amphoteric Metal Hydroxide Oscillations and Pattern Formation in Hydrogels.

Abstract

Oscillations in animate and inanimate systems are ubiquitous phenomena driven by sophisticated chemical reaction networks. Non-autonomous chemical oscillators have been designed to mimic oscillatory behavior using programmable syringe pumps. Here, we investigated the non-autonomous oscillations, pattern formation, and front propagation of amphoteric hydroxide (aluminum (III), zinc (II), tin (II), and lead (II)) precipitates under controlled pH conditions. A continuous stirred-tank reactor with modulated inflows of acidic and alkaline solutions generated pH oscillations, leading to periodic precipitation and dissolution of metal hydroxides in time. The generated turbidity oscillations exhibited ion-specific patterns, enabling their characterization through quantitative parameters such as peak width (W) and asymmetry (As). The study of mixed metal cationic systems showed that turbidity patterns contained signatures of both hydroxides due to the formation of mixed hydroxides and oxyhydroxides. The reaction-diffusion setup in solid hydrogel columns produced spatial precipitation patterns depending on metal cations and their concentrations. Additionally, in the case of tin (II), a propagating precipitation front was observed in a thin precipitation layer. These findings provide new insights into precipitation pattern formation and open avenues for metal ion identification and further exploration of complex reaction-diffusion systems.