A dual-strategy for energy release from AP/Al via F-doped Cu₂O Catalysis: Synergistic effects of surface oxygen vacancies and Cu⁺

Defect engineering has emerged as an effective strategy to enhance the physicochemical properties and catalytic performance of transition metal-based materials. However, its application in combustion catalysts for energetic materials remains insufficiently explored. In this study, high concentrations of oxygen vacancies were introduced into Cu₂O via nonmetallic fluorine doping to improve its catalytic performance in the thermal decomposition of ammonium perchlorate (AP) and the energy release of AP/Al formulations. Experimental characterizations and DFT simulations reveal that fluorine doping promotes the formation and thermal stability of oxygen vacancies, which remain abundant at 300 °C, enabling strong synergy with Cu active sites. As a result, the 1 wt% F-doped Cu₂O catalyst reduced the AP decomposition temperature by 105 °C and decreased the activation energy by 103.4 kJ/mol. Furthermore, it significantly enhanced the energetic performance of the AP/Al system, increasing the peak pressure by 461.8 kPa and accelerating the pressurization rate by a factor of 40.6. These findings highlight the promise of defect-engineered metal oxide catalysts for high-efficiency energetic applications.