All‐In‐One Ni/NiMoO _4−x Heterojunction with Tailored Electronic Band for Remarkably Elevated Type‐I Photodynamic/Photothermal/Chemodynamic Therapy

Type-I photodynamic therapy (PDT) with low oxygen dependence has drawn extensive attention in cancer therapy. However, the complex design of current type-I photosensitizers (PSs) brings great challenges to its clinical application, let alone develop type-I PDT-dominated "all-in-one" therapeutic nanoagents to further elevate anticancer efficacy. Herein, a novel defect-rich Ni/NiMoO_4-x nanorods is subtly designed as "all-in-one" therapeutic nanoagent for efficient cancer therapy. Unlike most type-I PSs with complicated synthesis, Ni/NiMoO_4-x is obtained by a facile hydrothermal-annealing method. The constructed active electronic states around Fermi level not only optimize the intrinsic Fenton-like activity of Ni/NiMoO_4-x, but also boost its light-harvesting capability and photoinduced electron generation. Additionally, the formed Schottky barrier directionally concentrates delocalized electrons on the modified ultrafine Ni nanoparticles to limit type-II PDT process. Moreover, the enriched electrons elevate photothermal effect induced by localized surface plasmon resonance of Ni metal. The Ni/NiMoO_4-x-driven "all-in-one" function, integrating specific type-I reactive oxygen species (ROS) production, chemodynamic therapy (CDT), photothermal therapy (PTT) and glutathione (GSH) depletion, results in satisfactory tumor suppression efficacy on 4T1-tumor-bearing mice with negligible toxicity to normal tissues, and can induce ferroptosis. This work holds great promise for the rational design of new high-performance type-I PSs.