Electrochemical Alcohol and Aldehyde Oxidation

References

Keywords

Rate Deconvolution Procedure J. Am. Chem. Soc. 2020, 142, 51, 21538–21547

Quantum-ESPRESSO J. Am. Chem. Soc. 2020, 142, 51, 21538–21547

Schematic Mechanism https://www.nature.com/articles/s41467-020-18461-1, https://pubs.acs.org/doi/full/10.1021/acscatal.1c04163

1. NonAqueous Electrolyte

2. Aqueous Electrolyte

2.1. References

1. Unraveling Two Pathways for Electrochemical Alcohol and Aldehyde Oxidation on NiOOH J. Am. Chem. Soc. 2020, 142, 51, 21538–21547

2.2. Experiments

Linear sweep voltammetry (LSV) was performed with a 3-electrode setup in an undivided cell made of glass. Ni(OH)2 films were used as the WE, Ag/AgCl as the RE and Pt as the CE. The potential was swept from the open circuit in the positive direction at a scan rate of 10 mV/s. Electrolyses were performed in a sealed, divided cell and employed the same 3-electrode setup as was used for the LSVs. The pH 13 KOH alcohol or aldehyde solution was added to the WE compartment while pH 13 KOH was added to the CE compartment. Then, 0.55 V vs Ag/AgCl was maintained potentiostatically until 33.3% of the charge required for the full conversion of alcohol or aldehyde into the carboxylic acid was passed. An exception to this is that for the much more concentrated 200 mM EtOH and 200 mM butanol solutions 6.5% of the charge required for full conversion was passed. We chose to pass only a portion of the charge required for full conversion when conducting these electrolyses to ensure that the results provided a more accurate reflection of the selectivities and Faradaic efficiencies that would have been present during the rate deconvolution experiments, as those were conducted at a substrate concentration equal to the concentrations at the beginning of the electrolyses. Additionally, doing so minimized the risk that any of the aldehydes would undergo degradation during the course of a longer electrolysis in the highly alkaline reaction solution. For the 200 mM EtOH and 200 mM butanol solutions, the smaller 6.5% of charge was used to keep the electrolysis times comparable across the different solutions.^{[J. Am. Chem. Soc. 2020, 142, 51, 21538–21547]}

2.2.4. Equation

2.3. Determination

2.4. Calculation of the yield, conversion rate, selectivity, and Faradaic efficiency