Sustainable electrosynthesis of energetic materials: Molecular precision to industrial adaptation - progress and limitations

Conventional synthesis methods, relying on strong acids and high-temperature conditions, suffer from issues such as high pollution, energy consumption, and safety hazards. However, electrochemical synthesis enables precise control of redox pathways through electron transfer, eliminating the use of toxic reagents and significantly reducing waste discharge and energy consumption. This review systematically summarizes the technological advancements, reaction mechanisms, and industrial application challenges of electrochemical synthesis for EMs. The article details various electrochemical strategies, including the efficient preparation of inorganic energetic materials (e.g., copper azide, EMs), C-N/N-N coupling for organic energetic molecules (e.g., o-diamines and azo compounds), and acid-free nitration of aromatic compounds via electrochemical nitration. Furthermore, it introduces the electrochemical synthesis and performance optimization of azaheterocyclic energetic compounds. Despite the remarkable advantages in selectivity, yield, and green chemistry, electrochemical synthesis faces challenges in the precise synthesis of complex molecules, large-scale continuous production, and catalyst stability. Future research should focus on designing advanced electrode materials (e.g., single-atom catalysts), integrating in-situ characterization with theoretical simulations to unravel reaction mechanisms, and coupling with clean energy technologies (e.g., electrolytic water for hydrogen production) to develop multifunctional integrated systems. This review presents electrochemical synthesis as a sustainable and precise Strategy for manufacturing energetic materials (EMs), circumventing the pollution and hazards of conventional acid- and heat-intensive step. It showcases core strategies including the preparation of inorganic EMs (e.g., copper azide), C–N/N–N coupling for building organic frameworks like azo compounds, and acid-free nitration of aromatics. Current challenges in catalyst selectivity, stability for continuous operation, and industrial scale-up are discussed. Future prospects emphasize advanced electrode design (e.g., single-atom catalysts), elucidating mechanisms via in-situ techniques, and coupling with clean energy technologies like water electrolysis to enable efficient, integrated production systems. • Electrochemical synthesis provides a green, precise alternative to conventional methods for energetic materials, replacing toxic reagents and reducing waste and energy consumption. • Key advances include electrochemical azidation, C–N/N–N coupling, and acid-free nitration, improving selectivity, yield, and performance of energetic compounds. • Future challenges involve complex molecule synthesis, scale-up, and catalyst stability, requiring advanced electrodes, in-situ studies, and clean energy integration.