(490d) Electrocatalytic Reductive Amination for Synthesis of Primary Amines
AIChE Annual Meeting
2020
2020 Virtual AIChE Annual Meeting
Catalysis and Reaction Engineering Division
Nitrogen Chemistry II: Nitrate & Nitrite Reduction
Thursday, November 19, 2020 - 8:45am to 9:00am
In this work, we found that ammonia and benzaldehyde can be reacted under a reductive electrochemical potential to form benzyl amine. This reaction proceeds through an inner-sphere pathway that is extremely solvent and catalyst dependent. We achieved partial currents across metals ranging from 0.5 mA/cm2 to over 3 mA/cm2 and Faradaic efficiencies ranging from below 10% to above 70%, and we have developed a theoretical descriptor that describes the influence of catalyst on electrochemical activity. We also interrogated the mechanism for this reaction and found that the first electron transfer is the rate-determining step and that the reaction exhibits non-linear dependencies on some reactants such as the benzaldehyde substrate, indicating complexities arising from surface adsorbates and secondary reaction products. Through mechanistic understanding of this inner-sphere reaction, we can suggest routes toward improving its selectivity and expanding substrate scope to other nitrogen-containing chemicals.