Electrochemical Strategy for Hydrazine Synthesis: Development and Overpotential Analysis of Methods for Oxidative N–N Coupling of an Ammonia Surrogate
| Autor: | Fei Wang, Yeon Jung Kim, James B. Gerken, Desiree M. Bates, Shannon S. Stahl |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
Molecular Structure
Chemistry Hydrazine Imine Inorganic chemistry Electrochemical Techniques General Chemistry Overpotential 010402 general chemistry Electrochemistry 01 natural sciences Biochemistry Redox Article Catalysis 0104 chemical sciences Azine chemistry.chemical_compound Hydrazines Colloid and Surface Chemistry Ammonia Benzophenone Thermodynamics Oxidative coupling of methane Oxidation-Reduction |
| Zdroj: | J Am Chem Soc |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.0c04626 |
| Popis: | 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 include (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. |
| Databáze: | OpenAIRE |
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