Dynamic Breaking the Covalency of Ru─O Bonds via Electronic Asymmetry Engineering for Efficient pH‐Universal Hydrogen Evolution

Abstract Dynamically self‐adaptive optimizing the local microenvironment of Ru─O bonds to enhance the adsorption of the *H is crucial for the efficient catalytic process. However, the limited regulatory strategies are unable to spontaneously control the Ru─O reconstruction process, thereby preventing the competitive adsorption of key intermediates at the catalytic active sites. Herein, an electronic asymmetry engineering is proposed by Ru single atoms coordinate with P and O atoms to create a local asymmetric O─Ru─P moiety, achieving dynamic optimization of Ru─O bond under the potential driven state during the HER process. The resultant Ru SA ─CoP electrocatalyst exhibits remarkable overpotentials of 15, 38, and 36 mV at a current density of 10 mA cm −2 in alkaline, acidic, and neutral media. Advanced in‐situ characterization reveals that the asymmetric O─Ru─P sites can modulate electron redistribution under the potential‐driven conditions, which achieves dynamic optimization of Ru─O bonds and strengthens Ru─H bonding interactions. More importantly, when the voltage is removed, the Ru─O bond is clearly observed again, which reveals the dynamic adaptation of Ru─O coordination during the reaction process. This work reveals the influence of the dynamic coordination evolution and structural adaptability of electrocatalysts on catalytic performance, providing valuable ideas for the design and synthesis of efficient electrocatalysts.