Curvature-Controlled Field Effect Enables Thermal Localization for Low-Temperature C─F Bond Activation.

Geometric singularities are known to concentrate electric and optical fields, but whether curvature alone can localize thermal energy and thereby influence chemical kinetics remains unresolved. Here, we show experimentally and computationally that nanoscale curvature generates localized thermal fields that directly lower reaction barriers in heterogeneous catalysis. Using γ-Al2O3 architectures with systematically varied curvature, nanoneedles, micro-needles, and spheres, while maintaining comparable composition, phase, acidity, and defect states, we observe curvature-dependent temperature localization of up to ∼30 °C at nanoneedle tips under identical external heating. In situ infrared thermography confirms hotspot formation, and operando vibrational spectroscopy reveals enhanced water dissociation and increased *CF3 intermediate populations during CF4 decomposition. These effects reduce the apparent activation energy and enable complete CF4 decomposition at 580 °C, substantially below that required for lower-curvature structures. The results establish curvature-induced thermal localization as a general physical mechanism linking geometry to interfacial energy density and reaction kinetics, providing a universal design principle for activating strongly bound molecules.