Decoupling OH and H Binding via Dual‐Site Conductive MOFs for Efficient Alkaline Hydrogen Evolution

ABSTRACT Efficient regulation of the hydrogen and hydroxyl binding energies (HBE/OHBE) lies at the core of developing high‐performance alkaline hydrogen evolution reaction (HER) electrocatalysts, yet it remains challenging due to the inherent correlation between the two binding energies. Herein, we demonstrate a d ‐electron modulation strategy on dual‐metal sites to break the scaling constraint and synergistically optimize HBE and OHBE. A well‐defined Cu‐based two‐dimensional conductive metal–organic framework (Cu‐HHTP) serves as a universal host to incorporate various 3 d transition metals (Mn, Fe, Co, Ni, Cu), yielding M–Cu dual sites with finely tunable d ‐electron configurations. Density functional theory calculations combined with experiments reveal that higher d ‐electron occupancy of the secondary metal site lowers the d ‐band center, and the water dissociation energy barrier exhibits a typical volcano‐type trend. The Co–Cu dual sites at the volcano apex promote the Volmer step through optimized OHBE and water adsorption. Meanwhile, this dual‐site configuration promotes the rearrangement of interfacial water molecules by disrupting the hydrogen‐bond network, thereby optimizing HBE. This work decouples HBE and OHBE via d ‐electron configuration, shifting the design paradigm from empirical screening to predictive design.