Open AccessElectrochemical Strategy for Hydrazine Synthesis: Development and Overpotential Analysis of Methods for Oxidative N–N Coupling of an Ammonia Surrogate
Author(s) -
Fei Wang,
James B. Gerken,
Desiree M. Bates,
Yeon Jung Kim,
Shan S. Stahl
Publication year - 2020
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.0c04626
Subject(s) - chemistry , benzophenone , azine , imine , electrochemistry , hydrazine (antidepressant) , ammonia , inorganic chemistry , redox , photochemistry , combinatorial chemistry , organic chemistry , catalysis , electrode , chromatography
Hydrazine is an important industrial chemical and fuel that has attracted considerable attention for use in liquid fuel cells. Ideally, hydrazine could be prepared via direct oxidative coupling of ammonia, but thermodynamic and kinetic factors limit the viability of this approach. The present study evaluates three different electrochemical strategies for the oxidative homocoupling of benzophenone imine, a readily accessible ammonia surrogate. Hydrolysis of the resulting benzophenone azine affords hydrazine and benzophenone, with the latter amenable to recycling. The three different electrochemical N-N coupling methods are (1) a proton-coupled electron-transfer process promoted by a phosphate base, (2) an iodine-mediated reaction involving intermediate N-I bond formation, and (3) a copper-catalyzed N-N coupling process. Analysis of the thermodynamic efficiencies for these electrochemical imine-to-azine oxidation reactions reveals low overpotentials (η) for the copper- and iodine-mediated processes (390 and 470 mV, respectively), but a much higher value for the proton-coupled pathway (η ≈ 1.6 V). A similar approach is used to assess molecular electrocatalytic methods for electrochemical oxidation of ammonia to dinitrogen.