F-centre charge state and dynamism govern oxide electrocatalytic selectivity

Oxygen vacancies tune electronic structure and can steer electrocatalysis, yet their intrinsic charge state, identifiable as different F centres, remains a largely untapped lever. Here we devise a template-assisted, atmosphere-regulated route to ZrO_2-x that keeps the crystal structure identical while varying the oxygen vacancy charge state, specifically electropositive F¹ centres and electroneutral F² centres, enabling a clean assessment of the impact on electrocatalytic selectivity. In situ electrochemical electron paramagnetic resonance tracking F-centre paramagnetism, together with in situ Raman of intermediate evolution, reveals that electroneutral F² is not the primary adsorption site. Rather, its dynamic electronic compensation to adjacent sites is crucial to the adsorption and evolution of *OOH. This triggers the 2e^- oxygen reduction reaction pathway. By contrast, electropositive F¹ directly binds O₂, causing O-O bond cleavage and subsequent quenching of the F¹ centre. These findings establish charge-state-governed catalysis by distinct F centres and provide a new perspective for vacancy engineering in electrocatalyst design.