Graphdiyne oxide-mediated remote regulation of ruthenium single-atom electronic structure by metal cations: Facilitating the performance enhancement of zinc-air batteries

The electronic structure modulation of single-atom catalysts (SACs) has traditionally depended on direct interactions with individual atoms to alter their electronic characteristics. However, the challenge of achieving atomically precise modulation of the coordination environment of single atoms limits the predictability of catalytic performance. In contrast to traditional local coordination engineering, which is restricted to short-range modifications, we propose a non-contact long-range regulation strategy utilizing graphdiyne oxide (GDYO). In this approach, carboxyl groups coordinate with metal cations to modulate the extended π-system, serving as an electronic transmission bridge for remote charge redistribution. This non-contact design facilitates the precise tuning of the electronic structure of Ru single atoms through long-range π-system mediation, without altering their local coordination environment. Consequently, this method enables the remote reconfiguration of the electronic structure of anchored ruthenium (Ru) single atoms while preserving their local coordination. The optimized Co²⁺/GDYO-Ru catalyst exhibits improved performance in oxygen reduction (ORR) and evolution reaction (OER). ZABs assembled with Co²⁺/GDYO-Ru demonstrate a 38 % increase in power density, a 41 % enhancement in specific capacity, and exceptional stability exceeding 2000 h—five times that of the control. Mechanistic studies reveal that cobalt-induced charge redistribution optimizes the Ru electronic configuration, facilitating *OH desorption in the rate-determining step via an upshifted d-band center. This work offers a universal approach for precise long-range regulation of the properties of SACs, breaking the spatial limitation of conventional local coordination engineering.