Deciphering Evolution Pathway of Supported NO3• Enabled via Radical Transfer from •OH to Surface NO3– Functionality for Oxidative Degradation of Aqueous Contaminants

NO₃ ^• can compete with omnipotent ^•OH/SO₄ ^•- in decomposing aqueous pollutants because of its lengthy lifespan and significant tolerance to background scavengers present in H₂O matrices, albeit with moderate oxidizing power. The generation of NO₃ ^•, however, is of grand demand due to the need of NO₂ ^•/O₃, radioactive element, or NaNO₃/HNO₃ in the presence of highly energized electron/light. This study has pioneered a singular pathway used to radicalize surface NO₃ ^- functionalities anchored on polymorphic α-/γ-MnO₂ surfaces (α-/γ-MnO₂-N), in which Lewis acidic Mn^2+/3+ and NO₃ ^- served to form ^•OH via H₂O₂ dissection and NO₃ ^• via radical transfer from ^•OH to NO₃ ^- (^•OH → NO₃ ^•), respectively. The elementary steps proposed for the ^•OH → NO₃ ^• route could be energetically favorable and marginal except for two stages such as endothermic ^•OH desorption and exothermic ^•OH-mediated NO₃ ^- radicalization, as verified by EPR spectroscopy experiments and DFT calculations. The Lewis acidic strength of the Mn^2+/3+ species innate to α-MnO₂-N was the smallest among those inherent to α-/β-/γ-MnO₂ and α-/γ-MnO₂-N. Hence, α-MnO₂-N prompted the rate-determining stage of the ^•OH → NO₃ ^• route (^•OH desorption) in the most efficient manner, as also evidenced by the analysis on the energy barrier required to proceed with the ^•OH → NO₃ ^• route. Meanwhile, XANES and in situ DRIFT spectroscopy experiments corroborated that α-MnO₂-N provided a larger concentration of surface NO₃ ^- species with bi-dentate binding arrays than γ-MnO₂-N. Hence, α-MnO₂-N could outperform γ-MnO₂-N in improving the collision frequency between ^•OH and NO₃ ^- species and in facilitating the exothermic transition of NO₃ ^- functionalities to surface NO₃ ^• analogues per unit time. These were corroborated by a greater efficiency of α-MnO₂-N in decomposing phenol, in addition to scavenging/filtration control runs and DFT calculations. Importantly, supported NO₃ ^• species provided 5-7-fold greater efficiency in degrading textile wastewater than conventional ^•OH and supported SO₄ ^•- analogues we discovered previously.