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Enhanced titanocene (Cp2TiCl2) based electrocatalytic system for nitrogen reduction was shown, comprising glassy carbon electrode, high level of the catechol redox mediator, optimized binary THF/MeOH solvent and unique design of the reactor having ammonia permeable membrane at the outlet, which allowed constant nitrogen flow through the working solution during entire electrolysis without risk of evaporation of the solvent. Catalytic activity was observed in the potential range of (−1.5)–(−2.3) V, reaching TON of 2.83%, corresponding to the production of 0.566 μmol NH3 (9.64 μg) in 24 h hydrolysis at −2.3 V using 0.02 mmol TiCp2Cl2 (5 mg).

Enhanced Activity of Titanocene Complex for Electrocatalytic Nitrogen Reduction Reaction