Electrochemical Strategy for Hydrazine Synthesis: Development and Overpotential Analysis of Methods for Oxidative N–N Coupling of an Ammonia Surrogate

Wang, Fei; Gerken, James B.; Bates, Desiree M.; Kim, Yeon Jung; Stahl, Shannon S.

doi:10.1021/jacs.0c04626

Electrochemical Strategy for Hydrazine Synthesis: Development and Overpotential Analysis of Methods for Oxidative N–N Coupling of an Ammonia Surrogate

Journal Article · Wed Jun 10 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c04626· OSTI ID:1647753

^[1]; Gerken, James B. ^[2]; Bates, Desiree M. ^[2]; Kim, Yeon Jung ^[2]; ^[2]

Univ. of Wisconsin, Madison, WI (United States); University of Wisconsin-Madison
Univ. of Wisconsin, Madison, WI (United States)

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. Here, 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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15690

OSTI ID:: 1647753

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 28 Vol. 142; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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