Boosting Photo‐Pyroelectric Effect via Tunable Polarization and Interfacial Defect Engineering

. Interface engineering introduces oxygen vacancies that enhance NIR-II photothermal conversion and serve as reactive sites to facilitate the dissociation of water molecules. Density functional theory calculations reveal that Zr doping narrows the bandgap and redistributes conduction band electrons, while interfacial oxygen vacancies facilitate water adsorption through optimized hydroxyl binding. As a result, synergistic pyrocatalysis and peroxidase-like activity under NIR-II-driven mild thermal cycling enable robust multipath ROS generation. Both in vitro and in vivo studies confirm efficient tumor cell ablation via NIR-II induced pyroelectric therapy. This work presents a co-engineering strategy integrating polarization and interface design to overcome long-standing limitations in pyroelectric catalysis, advancing its application in precision oncology.