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.

中文翻译：

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通过从 •OH 到表面 NO3 的自由基转移来破译支持的 NO3• 的进化途径– 用于水性污染物氧化降解的功能

NO ₃ ^•可以与万能的^• OH/SO ₄ ^•–在分解水性污染物方面竞争，因为它具有较长的使用寿命和对H ₂ O 基质中存在的背景清除剂的显着耐受性，尽管具有中等氧化能力。然而，由于在高能电子/光的存在下需要 NO ₂ ^• /O ₃、放射性元素或 NaNO ₃ /HNO ₃，因此产生 NO ₃ ^•的需求很大。这项研究开创了一种用于自由基化表面 NO ₃的单一途径^-锚定在多晶型 α-/γ-MnO 上的功能_{2 个}表面 (α-/γ-MnO ₂ -N)，其中路易斯酸性 Mn ^2+/3+和 NO ₃ ^–用于形成^• OH 通过 H ₂ O ₂分解和 NO ₃ ^•通过自由基从^• OH转移到NO ₃ ^– ( ^• OH → NO ₃ ^• )，分别。为^• OH → NO ₃ ^•路线提议的基本步骤可能在能量上是有利的和边缘的，除了两个阶段，例如吸热^• OH 解吸和放热^• OH 介导的 NO₃ ^–自由基化，通过 EPR 光谱实验和 DFT 计算验证。α-MnO ₂ -N固有的Mn ^2+/3+物质的路易斯酸强度在α-/β-/γ-MnO ₂和α-/γ-MnO ₂ -N固有的那些中最小。因此，α-MnO的₂ -N提示的速率决定阶段^• OH→NO ₃ ^•路线（^• OH解吸）以最有效的方式，也如通过在能量势垒的分析证明与进行所需的^• OH → NO ₃ ^•路线。同时，XANES 和原位漂移光谱实验证实，与γ-MnO ₂ -N相比，α-MnO ₂ -N 提供了更高浓度的表面 NO ₃ ^-具有双齿结合阵列的物质。因此，α-MnO ₂ -N在提高^• OH 和 NO ₃ ^–物种之间的碰撞频率以及促进 NO ₃ ^–官能团向表面 NO ₃ ^•类似物的放热转变方面可以胜过 γ-MnO ₂ -N 。α-MnO ₂的更高效率证实了这些-N 在分解苯酚中，以及清除/过滤控制运行和 DFT 计算。重要的是，与我们之前发现的传统的^• OH 和支持的 SO ₄ ^•-类似物相比，支持的 NO ₃ ^•物质在降解纺织废水方面的效率提高了 5-7 倍。