Electrocatalytic Reaction Induced Colloidal Accumulation: The Role of Dielectrophoresis.

A surface-driven flow is generated during the electrocatalytic reaction of a platinum-gold bielectrode within hydrogen peroxide. This flow can be experimentally visualized and quantified using micrometer-sized particles that are transported by a flow field. Tracer particles, which possess an inherent surface charge, also interact with the induced electric field and exhibit a collective behavior at the surface of the electrodes where they accumulate. The underlying mechanism for the accumulation dynamics demonstrated by these catalytic pump systems has so far been lacking. In this work, the accumulation dynamics and kinetics were experimentally investigated. With use of numerical simulations, we demonstrate that the self-driven particle accumulation is controlled by a positive dielectrophoretic force, mediated by the reaction-induced electric and flow field. These results contribute to the fundamental knowledge on immobilized bimetallic systems.

Electrocatalytic Reaction Driven Flow: Role of pH in Flow Reversal.

Immobilized bimetallic structures generate fluid flow during electrocatalytic reactions with hydrogen peroxide, which is typically driven from the anodic metal to the cathodic metal similar to an electroosmotic flow. However, under low reactive regimes, the generated flow becomes fully reversed, which cannot be explained by the classical electroosmotic theory. This work aims at unraveling the origin and dynamics of this flow hysteresis through a combined experimental and numerical approach. The key electrocatalytic parameters that contribute to flow reversal are analyzed experimentally and numerically under low reactive regimes induced by bulk pH variations. The proton gradient that initiates chemomechanical actuation is probed with the use of fluorescence lifetime imaging. The fluid flow dynamics under reactive regimes are visualized by the use of particle tracking. Our numerical simulations elucidate the role of pH variations and additional ionic species (counterions) toward flow reversal. The combination of these techniques highlights the interplay between electrocatalytic and electrokinetic phenomena on the occurrence of flow reversal.