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

Abstract 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.