Engineering Electronic Band Structure of Binary Thermoelectric Nanocatalysts for Augmented Pyrocatalytic Tumor Nanotherapy

Abstract Photothermal therapy (PTT) has emerged as a distinct therapeutic modality owing to its noninvasiveness and spatiotemporal selectivity. However, heat‐shock proteins (HSPs) endow tumor cells with resistance to heat‐induced apoptosis, severely lowering the therapeutic efficacy of PTT. Here, a high‐performance pyroelectric nanocatalyst, Bi₁₃S₁₈I₂ nanorods (NRs), with prominent pyroelectric conversion and photothermal conversion performance for augmented pyrocatalytic tumor nanotherapy, is developed. Canonical binary compounds are reconstructed by inserting a third biocompatible agent, thus facilitating the formation of Bi₁₃S₁₈I₂ NRs with enhanced pyrocatalytic conversion efficiency. Under 808 nm laser irradiation, Bi₁₃S₁₈I₂ NRs induce a conspicuous temperature elevation for photonic hyperthermia. In particular, Bi₁₃S₁₈I₂ NRs harvest pyrocatalytic energy from the heating and cooling alterations to produce abundant reactive oxygen species, which results in the depletion of HSPs and hence the reduction of thermoresistance of tumor cells, thereby significantly augmenting the therapeutic efficacy of photothermal tumor hyperthermia. By synergizing the pyroelectric dynamic therapy with PTT, tumor suppression with a significant tumor inhibition rate of 97.2% is achieved after intravenous administration of Bi₁₃S₁₈I₂ NRs and subsequent exposure to an 808 nm laser. This work opens an avenue for the design of high‐performance pyroelectric nanocatalysts by reconstructing canonical binary compounds for therapeutic applications in biocatalytic nanomedicine.