Rationally Designed S‐Doped Pd/ZnInO x for Enhanced Photothermal CO 2 Conversion

ABSTRACT Photothermal CO 2 conversion to CO offers a promising pathway toward net‐zero carbon management. Herein, we report an S‐doped Pd/ZnInO x photothermal catalyst derived from ZnIn 2 S 4 via a solid‐state reduction strategy. The catalyst exhibits high activity and stability for photothermal CO 2 conversion, yielding 28% conversion and ∼100% CO selectivity at 350°C under 0.8 W·cm −2 irradiation. S doping significantly reduces the apparent activation energy of Pd/ZnInO x from 108.52 to 65.42 kJ·mol −1 . Spectroscopic characterizations reveal that sulfur doping effectively modulates the band structure and electronic distribution, thereby enhancing light absorption while promoting the separation and migration of photogenerated charge carriers. In situ DRIFTS confirms that microreactors induced by S‐doped Pd/ZnInO x induces a localized microenvironment that facilitates the enrichment of * CO 3 2− and * CO intermediates. This work elucidates the pivotal role of S‐induced electronic structure modulation and interfacial synergistic effects in photothermal CO 2 conversion, offering new insights into the rational design of highly efficient photothermal catalytic systems.