Enhanced Spin-Engineering Photothermoelectric-Enzymatic Catalysis System via Lattice Mismatch-Induced Jahn-Teller...

Oxygen-dependent electrodynamic therapy is hindered by electron-hole recombination and hypoxia. This study provides a heterojunction-induced Jahn-Teller distortion-enhanced spin-engineering Fe₃O₄-Ag₂S nanoplatform to address these limitations. The large interfacial lattice mismatch induces previously unrecognized Jahn-Teller distortions on high-spin Fe sites, modifying d-orbital splitting and enhancing spin-polarized catalytic activity. This lattice-spin-carrier coupling synergistically amplifies catalase-, peroxidase-, and glutathioneox-like pathways. Under near-infrared irradiation, the photothermal effect of Fe₃O₄ activates the thermoelectric response of Ag₂S and drives continuous hot-carrier injection. Thermoelectric fields drive hot holes to boost catalase activity through Jahn-Teller effect-enhanced spin catalysis sites and drive hot electrons to convert O₂  to cytotoxic O₂^.- and ¹O₂ under the Jahn-Teller distortion, promoting and forming a self-amplifying catalytic loop. Fine structure characterization and density functional theory calculations collectively verify strain-driven Fe-O bond differentiation and spin-state reconfiguration. The heterojunction achieves potent thermoelectric-enzyme co-catalysis with 95% tumor inhibition under near-infrared irradiation and supports dual-mode imaging. This work establishes a framework for designing high-performance photothermal-thermoelectric catalysts through crystal field/spin-state modulation in p-n heterojunctions, synergistically boosting multi-enzyme activity and catalytic efficiency for hypoxia-resistant therapy.