Science advances

Electrochemical hydrogenation (ECH) of unsaturated carbon-heteroatom bonds is essential for chemical transformations but is often limited by a barrier-intensive surface hydrogen transfer process. The interfacial hydrogen bond (HB) network offers a promising pathway for proton transfer but requires addressing the challenge of nondirectional proton shuttling in three-dimensional space. Here, we create hydrophilic CuOx islands on Cu foam (CF) and load electron-enriched Pd (Pdδ-) single atoms as proton traps (Pd1-CuOx/CF) to guide a fast proton transfer along a modified HB network to enhance ECH efficiency. During ECH, hydrophilic CuOx islands dissociate H2O into protons and reconstruct the interfacial HB network for facile proton transfer, while the Pdδ- single atoms reorient H2O molecules to electrostatically attract and reduce protons to active hydrogen, enabling efficient substrate hydrogenation. With guided proton transfer, Pd1-CuOx/CF achieves 99% hydrogenation efficiency for C─Cl bonds, outperforming Pd1-CF (69%) and CuOx/CF (57%), and demonstrates high selectivity and Faradaic efficiency in hydrogenating C═O and C≡N bonds to produce valuable chemicals.