Nanoarchitectonics‐Enabled Stimulus‐Selective Energetics: Nacre‐Mimetic Interfaces Synchronize Structural Resilience and Enhanced Energy Release

Abstract The practical application of Metastable Intermolecular Composites (MICs) has long been constrained by an intrinsic trade‐off: the high specific surface area required for rapid energy release inevitably induces extreme sensitivity and structural fragility, while conventional stabilizing additives compromise energy density. To resolve this, we present a bio‐inspired geometric‐interfacial nanoarchitectural strategy. Hierarchically ordered films were engineered via the oriented assembly of 2D flake aluminum (F‐Al) and flake copper oxide (F‐CuO) into a nacre‐mimetic “brick‐and‐mortar” architecture. This design enhances stimulus‐specific response: edge stress concentration in F‐Al reduces thermal ignition thresholds by >40%, while percolating conductive networks increase electrostatic safety by 73%. Mechanically, the architecture improves strength and toughness by >300% through crack deflection and frictional dissipation. Furthermore, energy release efficiency is amplified, achieving an 8‐fold increase in flame propagation (128 mm s −1 ) driven by anisotropic thermal conduction and fluorine‐mediated interface activation. This work establishes geometric‐interfacial nanoarchitectonics as a paradigm to synchronize stress, charge, and heat transport, enabling next‐generation energetic materials for aerospace and Micro‐Electromechanical Systems (MEMS).