Long-range transport and directed assembly of charged colloids under aperiodic electrodiffusiophoresis†
Abstract
Faradaic reactions often lead to undesirable side effects during the application of electric fields. Therefore, experimental designs often avoid faradaic reactions by working at low voltages or at high frequencies, where the electrodes behave as ideally polarizable. In this work, we show how faradaic processes under ac fields can be used advantageously to effect long-range transport, focusing and assembly of charged colloids. Herein, we use confocal microscopy and ratiometric analysis to confirm that ac fields applied in media of low conductivity induce significant pH gradients below and above the electrode charging frequency of the system. At voltages above 1 Vpp, and frequencies below 1.7 kHz, the pH profile becomes highly nonlinear. Charged particles respond to such conditions by migrating towards the point of highest pH, thereby focusing tens of microns away from both electrodes. Under the combination of oscillating electric fields and concentration gradients of electroactive species, particles experience aperiodic electrodiffusiophoresis (EDP). The theory of EDP, along with a mass transport model, describes the dynamics of particles. Furthermore, the high local concentration of particles near the focusing point leads to disorder–order transitions, whereby particles form crystals. The position and order within the levitating crystalline sheet can be readily tuned by adjusting the voltage and frequency. These results not only have significant implications for the fundamental understanding of ac colloidal electrokinetics, but also provide new possibilities for the manipulation and directed assembly of charged colloids.