The Dilemma of Supporting Electrolytes for Electroorganic Synthesis: A Case Study on Kolbe Electrolysis

Remarkably, coulombic efficiency (CE, about 50 % at 1 Farad equivalent), and product composition resulting from aqueous Kolbe electrolysis are independent of reactor temperature and initial pH value. Although numerous studies on Kolbe electrolysis are available, the interrelations of different reaction parameters (e.g., acid concentration, pH, and especially electrolytic conductivity) are not addressed. A systematic analysis based on cyclic voltammetry reveals that solely the electrolytic conductivity impacts the current–voltage behavior. When using supporting electrolytes, not only their concentration, but also the type is decisive. We show that higher concentrations of KNO3 result in reduced CE and thus in significant increase in electric energy demand per converted molecule, whereas Na2SO4 allows improved space–time yields. Pros and cons of adding supporting electrolytes are discussed in a final cost assessment. Salt in the electrosynthetic soup: Adding salts (supporting electrolytes) to aqueous solutions for electroorganic synthesis can solve and create dilemma related to reaction selectivity, space‐time yield, downstreaming, and electricity consumption. In this study, systematic analysis reveals that solely the electrolytic conductivity impacts the current–voltage behavior. The pros and cons of adding supporting electrolytes are discussed in a final cost assessment.