Catalysis-inspired d-band center engineering enables hydrogen-suppressed zinc anodes for long-life aqueous zinc-ion...

Aqueous zinc-ion batteries (AZIBs) are promising for energy storage. However, Zn anode instability-caused by dendrite growth, hydrogen evolution reaction (HER), and by-product formation-limits their practical viability. HER, in particular, accelerates Zn consumption, disrupts electrode integrity, and induces local alkalization, exacerbating passivation. Conventional strategies emphasize electrolyte formulation and surface passivation, yet few address the underlying electronic origin of HER on Zn. Here we report a catalysis-inspired strategy that electronically modulates Zn reactivity via d-band center engineering to intrinsically suppress HER. By introducing oxalic acid (OA) as a molecular additive, we achieve a significant downward shift in the Zn d-band center (from -6.896 to -7.062 eV), weakening hydrogen adsorption and fundamentally reducing HER activity. In parallel, OA disrupts the Zn²⁺ solvation structure by displacing coordinated SO₄^2- anions, suppressing interfacial by-product formation. These dual effects yield unprecedented performance: Zn||Zn symmetric cells operate stably for over 3500 h; Zn||Cu cells exhibit 99.41% Coulombic efficiency over 1500 cycles; and Zn||I₂ cell retain 92.8% capacity after 10,000 cycles; the 1.3 Ah Zn||I₂ pouch cell presents good cyclability. This work pioneers a surface electronic tuning paradigm in battery design, extending catalytic d-band theory to electrochemical interfaces for HER suppression and interfacial stabilization in aqueous metal batteries.