Visualizing the Zero-Potential Line of Bipolar Electrodes with Arbitrary Geometry.

In a typical bipolar electrochemistry (BPE) configuration, voltage applied between the two driving electrodes induced a potential drop through solution filled in the microchannel, resulting in an interfacial potential difference between solution and BPE varied along the BPE. In the present work, we employed a recently developed plasmonic imaging technique to map the distribution of surface potential of bipolar electrodes with various geometries including round, triangle, hexagon, star, and rhombus shapes under the nonfaradaic charging process, from which the line of zero potential (LZP) was visualized and determined. We further investigated the dependence of LZP on electrode geometry and the distribution of external electric field and explained the experimental results with a charge balance mechanism. The triangular and star-shaped BPEs show quite different LZP features from the other ones with symmetrical geometry. These experimentally obtained potential distributions are all in good agreement with electromagnetic simulations. Finally, the line of zero overpotential (LZO) of the triangular-shaped BPE under faradaic reactions were investigated. The results confirm the shift of LZO when faradaic reactions occurred at the corresponding ends of BPE. The present work demonstrates the first experimental capability to map the potential distribution of BPE with arbitrary geometry under an arbitrary driving field. It is anticipated to help the design and optimization on the geometry of electrodes and microchannels with implications for boosting their applications in chemical sensing and materials synthesis.