Leaf‐Architecture and Function‐Mimicked Ensemble of Hierarchical Ag Nanowires/Ti ₃ C ₂ T _x MXene@Sulfur‐Vacancy Rich ZnIn ₂ S ₄ Nanosheet Arrays for Enhanced Photoredox Catalysis

Abstract In pursuing efficient photocatalytic systems, nature‐inspired photocatalysis has emerged as a promising strategy to optimize charge transfer and surface reactions. Inspired by the structure and function of plant leaves, a leaf‐like hierarchical heterostructure is constructed. ZnIn ₂ S ₄ nanosheet arrays are anchored on the integrated Ag nanowires network with Ti ₃ C ₂ T _x MXene support, during which process sulfur vacancies (V _S ) are formed due to the anti‐strong metal‐support interaction. The ZnIn ₂ S ₄ nanosheet arrays supported by Ti ₃ C ₂ T _x serve as mesophyll to absorb photons and convert solar‐to‐chemicals, the Ag nanowires embedded in the interface of ZnIn ₂ S ₄ and Ti ₃ C ₂ T _x function as veins to shuttle the charge carriers for the surface redox reactions, and the V _S on ZnIn ₂ S ₄ resemble stomata to facilitate the adsorption of reactants. Furthermore, the formed V _S are able to reduce the thermodynamic barriers in photocatalytic reactions. The synergistic effect of these functional components enables hydrogenation of several nitroaromatic compounds, and exhibits a photocatalytic H ₂ evolution rate of 1119.4 µmol g⁻¹ h⁻¹ under visible‐light irradiation, which is ≈7.9 times as high as that of pure ZnIn ₂ S ₄ . This study highlights the pivotal role of functional design inspired by nature in advancing solar‐to‐chemical conversion and paves the way for the development of next‐generation photocatalysts in green chemistry and H ₂ energy applications.