Electrochemical Synthesis of High-Nitrogen Materials and Energetic Materials

Abstract

Electrochemical synthesis is a valuable method for the preparation of molecules. It is innately eco-friendly, as potentially hazardous oxidation and reduction agents are replaced with electrochemical potentials. Electrochemistry is commonly applied globally in the synthesis of numerous chemicals, but the energetic materials field lags in this regard. In this review, we endeavor to cover the entire history of synthetic electrochemistry for the preparation of energetic materials and detail the electrochemical transformations of high-nitrogen materials that are relevant for the preparation of new energetic molecules. We hope this review serves as a starting point to inform those involved in synthetic energetic materials chemistry, and those interested in other applications of high-nitrogen molecules, about the environmentally friendly electrochemical methods available for such compounds.

Green Electrosynthesis of 5,5′‐Azotetrazolate Energetic Materials Plus Energy‐Efficient Hydrogen Production Using Ruthenium Single‐Atom Catalysts

“…[14,23] However, only a few OEMs have been successfully obtained by facile electrochemical pathways; thus, OEM electrosynthesis lags behind the global electrochemical synthesis of numerous chemicals. [24] Yount et al demonstrated the successful electrooxidation of 3,4,5-triamino-1,2,4-triazole and yielded new OEMs with superior thermal stability and low sensitivity toward impact and friction. [14] Sheremetev et al reported the electrooxidation of aminofurazans to azofurazans on a nickel oxyhydroxide anode.…”

Intramolecular Assembly of Nitrobiazoles and an Ether Bridge: Toward Energetic Materials with Enhanced Energy and Safety

“…In the latest decades, owing to unique chemical properties and environmental friendliness, green nitrogen-rich insensitive high-energy density materials (HEDMs) for military and civilian applications have gained widespread research attention in the area of energetic materials. − As a unique class of novel HEDMs, fused cyclic energetic materials have been recognized as promising alternatives to conventional energetic materials. , Benefiting from considerably high heats of formation (HOF) and ring-strain energy, the fused-ring energetic compounds with a coplanar polycyclic structure usually show high detonation properties, improved thermostability, and significant insensitivity against external mechanical stimuli, which greatly increases the safety of the production, handling, transfer, and storage of new materials. However, the limited number of fused-ring frameworks available for the preparation of various molecules has severely hindered their further expansion in energetic materials chemistry.…”

Energetic Salts of Sensitive N,N′-(3,5-Dinitropyrazine-2,6-diyl)dinitramide Stabilized through Three-Dimensional Intermolecular Interactions

“…Over the past two decades, explosive growth of high-energy-density materials based on derivatives of five- or six-membered azines has occurred. − Energetic metal–organic frameworks (EMOFs) assembled from metallic nodes with nitrogen-rich azines have gained much interest because of their dense crystalline structures. − The preparation of EMOFs has undergone substantial advancement, from one-dimensional (1D) and two-dimensional (2D) EMOFs to the emergence of three-dimensional (3D) EMOFs. − Moreover, these 3D energetic frameworks possess more complex linking modes in comparison with 1D linear and 2D layered structures, which improves their structural reinforcement and molecular stabilities. − Nowadays, these 3D EMOFs play a central role in modern energetics because of their prevalent occurrence across a broad range of applications such as explosives, oxidizers, and pyrotechnics. , New EMOFs should preferably have good detonation properties, high density, and good thermal stability, along with ease of synthesis, high atom economy, and waste prevention. Therefore, tuning the structures and physicochemical properties of existing energetic structures by tailoring their properties for required applications is highly desirable …”