Unlocking Efficient Near‐Infrared CO 2 Photoreduction Over Metallic Photocatalysts Through Charge Polarization

Metallic photocatalysts provide a promising route for utilizing low‐energy near‐infrared (NIR) photons in CO 2 conversion because they bypass the bandgap constraints of conventional semiconductors. However, their intrinsically uniform electrostatic potential limits charge separation and CO 2 adsorption/activation, thereby restricting their photocatalytic performance. Here, we report a charge polarization strategy that addresses this bottleneck through the synergistic incorporation of sulfur vacancies ( S v ) and Au single atoms (Au SAs) in metallic NiCo 2 S 4 . The optimized Au SA / S v ‐NiCo 2 S 4 photocatalyst exhibits a 64‐fold enhancement in activity relative to pristine NiCo 2 S 4 under NIR irradiation without sacrificial agents, delivering CO and CH 4 production rates of 1020 and 150 µmol g −1 h −1 , respectively. Notably, it achieves a benchmark apparent quantum efficiency (AQE) of 1.24% at 800 nm and a solar‐to‐chemical energy conversion (STC) efficiency of 0.86% at room temperature. Mechanistic investigations reveal that charge redistribution reshapes the photocatalytic behavior of the metallic system in two complementary ways: it induces local polarization that suppresses charge recombination, and favors the formation of bimetallic Co 3+ ⋯Ni 2+ frustrated Lewis pair (FLP) sites for CO 2 adsorption, activation, and *COOH generation. This work demonstrates charge polarization as an effective strategy for designing metallic photocatalysts, opening new opportunities for efficient solar‐driven CO 2 valorization.