Electrochemistry‐Mediated Synthesis of Hydrazine from Ammonia

The synthesis of hydrazine from the electrooxidation of ammonia (NH₃) presents a promising pathway, yet it is hindered by the strong thermodynamic preference for the oxidation of hydrazine. Here, we describe an electrochemistry-mediated strategy that reverses the thermodynamic order during NH₃ oxidation, enabling sustainable hydrazine production. This process utilizes cyclohexanone (C₆H₁₀O), derived from the electrooxidation of cyclohexanol (C₆H₁₁OH), as a mediator to prevent the over-oxidation of NH₃. The in situ generation of cyclohexanone (C₆H₁₀O) at the catalyst interface effectively prevents the over-oxidation of NH₃, while cation effect accelerates NH₃ capture during the reaction. Furthermore, the developed manganese (Mn) doped nickel hydroxide electrocatalyst (Mn-Ni(OH)₂) not only improves NH₃ tolerance of the catalyst but also promotes the conversion of nitrogen-containing intermediates. This scalable approach achieves gram-scale production at a constant current of 800 mA, offering economic advantages over industrial methods, paving the way for a sustainable transformation of the chemical industry.