N ₂ Products of Ammonium Perchlorate Promoted by Anthraquinone-COF via Electron Transfer

Activating electron transfer channels in non-conductive materials remains a critical challenge for optimizing chemical reactions. For ammonium perchlorate (AP), a key oxidizer in solid propellants, opening electron transfer pathways is essential to enhance its decomposition efficiency and regulate product distribution. Herein, we report an anthraquinone-based covalent organic framework (COF) as a metal-free catalyst to facilitate electron transfer during AP decomposition. The COF catalyst, synthesized with a controllable flower-like morphology (COF-F), effectively activates electron transfer from ClO₄⁻ to NH₄⁺ in AP, as validated by experimental and theoretical results. Compared to pure AP, COF-F increases the decomposition rate by 22.5%, eliminates the "stagnation" stage between low-temperature decomposition (LTD) and high-temperature decomposition (HTD), and shifts the nitrogen-containing product distribution toward environmentally benign N₂ (52.4% vs 30.7% in pure AP). Density functional theory (DFT) calculations confirm that the conjugated structure of the COF bridges the energy gap between ClO₄⁻ and NH₄⁺, enabling efficient electron transfer. This work demonstrates the potential of anthraquinone-COFs in activating electron transfer in nonconductors, offering a strategy to improve propellant performance and reduce environmental impact.