Dynamic Hydrogen‐Bonding Nanonetworks and Asymmetric Dual‐Interface Built‐In Electric Fields Cooperatively Mediate Proton‐Coupled Electron Transfer for C─H Activation

ABSTRACT C─H bond activation represents a ubiquitous transformation in chemistry, yet challenging owing to the complex requirements for proton and electron transfer. A general strategy for constructing proton–electron dual‐transport‐channel photocatalysts: hollow hierarchical Co 3 S 4 /Sv‐chalcogenide/Ti 3 C 2 nanoreactors (Sv = sulfur vacancies, chalcogenide = CdIn 2 S 4 , ZnIn 2 S 4 , CdS) is developed via lateral epitaxy and defect‐mediated heterocomponent anchorage. These ternary‐component nanoreactors integrate dynamic hydrogen‐bonding nanonetworks and asymmetric dual‐interface built‐in electric fields (BIEFs), acting as the strong proton/electron extractors for steering proton‐coupled electron transfer (PCET) in C─H activation of biomass‐derived molecules. The BIEFs‐induced electron transport channel is featured by powerful photocarrier enrichment and feeble photocarrier recombination at Co 3 S 4 /chalcogenide S‐scheme heterointerface, and photocarrier localization and delocalized‐electron transport at Sv‐chalcogenide/Ti 3 C 2 Schottky heterointerface. The hydrogen bond network‐induced proton transport channel lies in electron‐enriched interfacial lattice oxygen for mediating the substrate deprotonation via nucleophilic abstraction, and the hydrophilic MXene for guiding proton transfer along modified dynamic hydrogen‐bonding nanonetworks. By virtue of dynamically optimized molecular catalytic behavior accomplished by pivotal intermediate adsorption/activation regulation, representative Co 3 S 4 /Sv‐CdIn 2 S 4 /Ti 3 C 2 HNR exhibits remarkable C─H activation performance and broad substrate compatibility. This work establishes a pioneering paradigm for manipulating proton–electron dual‐transport‐channel by hydrogen‐bonding nanonetworks and BIEFs, offering novel strategies for regulating molecular catalytic behavior in complex reaction pathways.