Cu2MoS4/Au Heterostructures with Enhanced Catalase‐Like Activity and Photoconversion Efficiency for Primary/Metastatic Tumors Eradication by Phototherapy‐Induced Immunotherapy

Photoimmunotherapy can not only effectively ablate the primary tumor but also trigger strong antitumor immune responses against metastatic tumors by inducing immunogenic cell death. Herein, Cu2MoS4 (CMS)/Au heterostructures are constructed by depositing plasmonic Au nanoparticles onto CMS nanosheets, which exhibit enhanced absorption in near‐infrared (NIR) region due to the newly formed mid‐gap state across the Fermi level based on the hybridization between Au 5d orbitals and S 3p orbitals, thus resulting in more excellent photothermal therapy and photodynamic therapy (PDT) effect than single CMS upon NIR laser irradiation. The CMS and CMS/Au can also serve as catalase to effectively relieve tumor hypoxia, which can enhance the therapeutic effect of O2‐dependent PDT. Notably, the NIR laser‐irradiated CMS/Au can elicit strong immune responses via promoting dendritic cells maturation, cytokine secretion, and activating antitumor effector T‐cell responses for both primary and metastatic tumors eradication. Moreover, CMS/Au exhibits outstanding photoacoustic and computed tomography imaging performance owing to its excellent photothermal conversion and X‐ray attenuation ability. Overall, the work provides an imaging‐guided and phototherapy‐induced immunotherapy based on constructing CMS/Au heterostructures for effectively tumor ablation and cancer metastasis inhibition. In CMS/Au heterostructure, the hybridization between Au 5d orbitals and S 3p orbitals contributes enormously to the densities of states near the Fermi energy, thus resulting in more excellent photothermal and photodynamic therapy effect than single CMS upon near‐infrared laser irradiation. Notably, the CMS/Au‐based phototherapy can elicit strong immune response for both primary and metastatic tumors eradication by phototherapy‐induced immunotherapy.