Proton‐Electron Dual‐Transfer‐Channel Nanoreactors for Proton‐Coupled Electron Transfer (PCET) in Photocatalytic Polyester Dehydrogenation‐Reductive Amination

Abstract The photocatalytic polyester‐to‐amino acid transformation is significant for waste upcycling, yet challenging owing to the intricate multiple proton and electron transfer processes required. Herein, a general strategy for synthesizing hollow core‐shell Sv‐chalcogenide/Ti ₃ C ₂ nanoreactors (Sv = sulfur vacancies, chalcogenide = CdS/ZnIn ₂ S ₄ /CdIn ₂ S ₄ ) is developed via templated epitaxial growth and defect‐mediated interfacial bond construction, which act as the strong proton/electron extractor and relay station for tandem proton‐coupled electron transfer (PCET) in photocatalytic polyester‐to‐amino acid dehydrogenation‐reductive amination. These nanoreactors integrate spatially segregated proton‐electron dual‐transfer channels, where the interfacial asymmetrical charge distribution‐induced built‐in electric field (BIEF) drives directional electron transfer (ET) from chalcogenide to Ti ₃ C ₂ , while the electron‐rich interfacial lattice oxygen mediates substrate deprotonation process via nucleophilic abstraction, delivering protons to Ti ₃ C ₂ and forming Ti ₃ C ₂ (OH)⁺ intermediates to trigger proton transfer (PT). By virtue of dynamically optimized molecular catalytic behavior accomplished through precise regulation of pivotal intermediate adsorption and activation energetics, the representative Sv‐CdS/Ti ₃ C ₂ hollow nanoreactor (HNR) exhibits remarkable performance (10 mmol·g ⁻¹ ·h ⁻¹ and 91% selectivity, alanine) and broad applicability for polyester‐derived hydroxy acid‐to‐amino acid transformation. This study establishes a pioneering paradigm for the design of proton‐electron dual‐transfer‐channel photocatalysts and provides novel perspectives for the effective regulation of complex reaction pathways.