Journal
CHEMSUSCHEM
Volume 9, Issue 1, Pages 50-60Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cssc.201501407
Keywords
cyclic voltammetry; electrochemical oxidation; electrolytes; electrolytic conductivity; electroorganic synthesis
Funding
- BMBF
- Helmholtz Association (Young Investigators Group)
- Helmholtz Association within the Research Programme Renewable Energies
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Remarkably, coulombic efficiency (CE, about 50% at 1Farad 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.
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