Hydroxyl-Mediated Electrochemical Dehydrogenative Coupling of 5-Aminotetrazole for Energetic Azotetrazolate Synthesis and Energy-Saving Hydrogen Production

Electrochemical synthesis offers a safe and sustainable route for synthesizing energetic materials (EMs). This work presents a green electrosynthetic strategy for 5,5′-azotetrazolate (ZT) by leveraging the low oxidation potential of 5-amino-1H-tetrazole (5-AT) in a coupled electrolysis system for energy-efficient hydrogen production. Anodic potassium 5,5′- azotetrazolate (PZT) synthesis is achieved using a CF@CuO catalyst, while cathodic hydrogen evolution is facilitated by a CC@VS2/Ru nanoparticle composite. The integrated system requires only 1.36 V to deliver 10 mA cm–2, which is 190 mV lower than that of conventional overall water splitting. The coupling strategy circumvents the use of strong oxidants and by-product formation inherent to traditional PZT synthesis, and the integrated electrolyzer exhibits stable continuous operation for over 50 h, while the CF@CuO anode maintains high 5-ATOR activity during a cumulative 300 h reusability test. Mechanistic investigations reveal that on the cathode side, Ru modification modulates the electronic structure of VS2, optimizing hydrogen adsorption free energy and accelerating water dissociation kinetics for enhanced alkaline HER. On the anode side, CuO catalyzes the 5-AT oxidation reaction (5-ATOR) via the OH*-mediated pathway, where continuous electron injection weakens N–H bonds and facilitates dehydrogenation coupling, significantly lowering the reaction energy barrier. This work establishes a dual-functional electrochemical platform integrating safe energetic materials synthesis with energy-saving hydrogen production.