Paired Electrosynthesis at Interdigitated Microband Electrodes: Exploring Diffusion and Reaction Zones in the Absence of a Supporting Electrolyte

Electrosynthesis traditionally requires dedicated reactor systems and an added electrolyte, although some paired electrosynthesis processes are possible at interdigitated microband electrodes simply immersed in solution and without an intentionally added electrolyte. Here, 1,1′-ferrocenedimethanol oxidation and activated olefin electro-hydrogenation reactions are investigated as model processes at a Pt–Pt interdigitated microband array electrode with 5 μm width and with 5 μm interelectrode gap. Voltammetric responses for electro-hydrogenation are discussed, and product yields are determined in methanol (MeOH) in the presence/absence of an added electrolyte (LiClO₄). An isotope effect is observed in CH₃OD solvent, leading to olefin monodeuteration linked to a fast EC-type process close to the cathode surface (in the cathode reaction zone) rather than to charge annihilation in the interelectrode zone. A finite element simulation is employed to visualize/discuss reaction zones and to contrast the rate of charge annihilation processes with/without a supporting electrolyte.