Unveiling a Redox‐Assisted Electrocatalysis Approach for Efficient Azo‐Based High‐Energy Material Synthesis

The azo reaction serves as a key approach for integrating high‐energy ─N═N─ linkages into energetic materials, enabling precise modulation of their energy output and structural properties. Herein, we systematically explored efficient synthesis strategies for the key energetic material 3,3′‐diamino‐4,4′‐azofurazan (DAAzF) through chemical, electrochemical, and coupled approaches. Chemical oxidation of 3,4‐diaminofurazan (DAF) using Ce 4+ achieved an optimal yield of 83.3% and 97.0% purity. A high‐performance Ni‒Co 3 O 4 @CC anode catalyst was developed, demonstrating excellent electrocatalytic activity for DAF oxidation (118.7 mA·cm ‒2 ) and long‐term stability (92.5% Faradaic efficiency after 15 h). To integrate the high yield of chemical synthesis with the environmental benefits of electrochemistry, an innovative coupled system based on the Ce 3+ /Ce 4+ redox pair was constructed. This modular closed‐loop design features an initial reaction chamber, a flow electrolysis cell, and a regeneration chamber, where Ce 4+ is efficiently regenerated on Ni‒Co 3 O 4 @CC for continuous DAF oxidation. Within 120 min, this coupled system achieved a remarkable cumulative DAAzF yield of 87.46% with 79.95% Faradaic efficiency, significantly outperforming the single electrochemical route (1.62% yield) and the single chemical route (83.3% yield). This work not only provides an innovative and sustainable synthesis pathway for DAAzF but also establishes a versatile green paradigm for preparing other azo‐containing energetic materials.