Polarization‐Selective Efficient Hydrogen Evolution Reactions via Chiral Photocatalysis

The growing demand for sustainable energy solutions has stimulated the development of advanced photocatalysts with enhanced efficiency of solar-driven hydrogen production. However, the intrinsic challenges of hydrogen evolution reaction (HER), including rapid electron-hole recombination, and insufficient light absorption of conventional semiconductors, underscore the need for innovative catalytic strategies beyond conventional semiconductors. Here, a chirality-integrated plasmonic photocatalyst synthesized via circularly polarized light (CPL)-guided growth of Au nanoparticles on g-C₃N₄, yielding R-Au/C₃N₄ and L-Au/C₃N₄ with opposite optical chirality is presented. R-Au/C₃N₄ under right-handed CPL (RCP) illumination exhibits a 2.10-fold increase in hydrogen evolution rate compared to under left-handed CPL (LCP), and a 1.71-fold improvement over achiral A-Au/C₃N₄. In-situ Fourier transform infrared spectroscopy (FTIR) and time-resolved photoluminescence (TRPL) analyses revealed that chirality-matched light-catalyst pairs (i.e., RCP irradiation on R-Au/C₃N₄ and LCP irradiation on L-Au/C₃N₄) effectively suppress energy transfer pathway, thereby enriching the excited electron population in g-C₃N₄ and subsequently accelerating HER. Ex-situ EXAFS measurements demonstrated that chiral matching conditions contribute to reinforcing the structural durability of the resulting chiral catalyst. This CPL-responsive platform establishes a new paradigm in photocatalyst design by coupling chirality with light-matter interaction toward efficient solar-to-hydrogen conversion.