Amidoxime-functionalized covalent organic framework for enhanced thermal decomposition of ammonium perchlorate

• Covalent organic frameworks material was introduced as catalyst for the thermal decomposition of AP. • The dioxin‐linked amidoxime-functionalized COF was synthesized. • The functionalized COF possessed abundant coordination active sites of Cu 2+ . • Cu-COF-316-AO displayed the admirable catalytic effect for the thermal decomposition of AP. The design of catalysts with consistent surface properties, controllable structures and efficient performance for thermal decomposition of ammonium perchlorate (AP) has been a challenge in the development of composite solid propellants. In this work, covalent organic frameworks (COFs) with the desired designability and functionality were introduced as catalyst in thermal decomposition of AP for the first time. We reported a dioxin‐linked two-dimension (2D) COF (COF-316) with excellent thermal and chemical stability, and COF-316-AO (COF-316-C(NOH)NH2) was obtained by a post-modification strategy through the amidoximation of nitrile in 1D channels. Both COF-316 and COF-316-AO exhibited catalytic activity for the thermal decomposition of AP, which reduced the decomposition temperature of AP by 50 °C and 22 °C, respectively, demonstrating the positive effect of COFs. The pre-engineered COFs possessed abundant coordination active sites of Cu 2+ , and the introduction of uniformly coordinated Cu 2+ to COFs (denoted as Cu-COF-316 and Cu-COF-316-AO) further enhanced the catalytic performance of the material. Cu-COF-316-AO with a higher Cu 2+ loading amount displayed the admirable catalytic effect, it reduced the decomposition temperature from 448 to 325°C and increased heat release by 1.7 times compared to pure AP, which confirmed that the abundance of coordinated Cu 2+ is proportional to catalysis the thermal decomposition of AP, indicating that the design of COFs can tune the catalytic decomposition effect of AP. This work introduced well-structured and easily functionalized COFs into AP decomposition, paving a pathway for research development of tunable AP decomposition catalytic materials.