Polarization‐Selective Efficient Hydrogen Evolution Reactions via Chiral Photocatalysis

Abstract

ABSTRACT 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‐C 3 N 4 , yielding R‐Au/C 3 N 4 and L‐Au/C 3 N 4 with opposite optical chirality is presented. R‐Au/C 3 N 4 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/C 3 N 4 . 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/C 3 N 4 and LCP irradiation on L‐Au/C 3 N 4 ) effectively suppress energy transfer pathway, thereby enriching the excited electron population in g‐C 3 N 4 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.