Catalytic engineering overrides practical performance limitations: Revolutionizing energetic material design via cerium-mediated kinetic pathway optimization

Overcoming the persistent challenge of incomplete combustion in aluminum-based energetic materials, this study introduces a catalytic engineering strategy that transcends conventional practical performance limitations. By incorporating aluminum-cerium (Al₂Ce) alloy into the ammonium perchlorate (AP) system, a dual-pathway mechanism that combines physical dispersion and chemical catalysis revolutionizes the energy release profile. Multiscale in situ characterization and first-principles calculations unveil that cerium directly participates in an exothermic redox reaction with the low-temperature decomposition intermediate of AP, HClO₄, leading to a dramatically exothermic process. The overall reaction energy on the Ce₂O₃ (0001) surface is approximately 6.09 eV more negative than that on the α-Al₂O₃ (0001) surface, indicating a much more kinetically favorable pathway and undergoing a Ce³⁺ to Ce⁴⁺ transition to form CeO₂. This in situ-generated porous CeO₂ disrupts the passivating Al₂O₃ layer, exposes fresh metallic interfaces, and establishes a self-sustaining thermal cycle. Remarkably, despite an 11.3% reduction in total calorific value, the combustion temperature surges by 15% to 2848°C, achieving near-complete aluminum combustion efficiency approaching 100% and generating monodisperse CeO₂/Al₂O₃ aerosols with exceptional stability (gas evolution <0.5 mL·g⁻¹). This work establishes cerium-mediated reaction pathway optimization as a novel design strategy, shifting the design principle of energetic materials from the sole pursuit of energy density maximization toward the catalytic engineering regulation of reaction kinetics.