During many electrochemical reactions, the electron transfer occurs at a solid–liquid interface, with water being the ideal liquid phase. Loss of solid–liquid contact area is a detrimental event. A common problem in aqueous electrochemistry is poor reaction kinetics due to the poor water solubility of chemical compounds; the same effect is observed with some organic solvents, such as acetonitrile. This work highlights how strategic electrode fouling with hydrophobic oil insulators can mitigate this issue, demonstrating that a loss of electrode area does not result in a loss of electrochemical efficiency. Firstly, a principal ruthenium-based electrochemiluminescent solution in acetonitrile is used to strategically fouling the electrode with hydrophobic oil insulators, we observed a huge enhancement in electrochemiluminescence at the insulator-electrode-electrolyte triple point, as determined by electrochemiluminescence microscopy. We demonstrate that this effect is due to centripetal fluid flow towards the insulator due to Marangoni effect, centripetal flow and density-driven convection significantly alter mass transport at the electrode. This centripetal flow is further supported by buoyancy resulting from acetonitrile density changes and gravity. The formation of a luminance halo suggests that the reaction zone shifts over time, thus providing a visual map of the general reaction zone and how this zone shifts over time. Thus, despite the reduction in electrode-electrolyte contact area, electrolysis rates are significantly enhanced due to this electrode design. Then an aqueous chiral solution using amino acids in a saline-phosphate buffered solution (PBS) with ruthenium will be used in tangent with insulators made of chiral building blocks to explore the feasibility of enantioselective adsorption reactions to perform chiral water-based electrochemistry on achiral electrodes by harvesting adsorption (rates and selectivity) and electroosmotic flow (rates) augmentation at the fouled electrodes.