羟基自由基在 NTO 降解中的作用：DFT 研究,The Journal of Physical Chemistry A

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羟基自由基在 NTO 降解中的作用：DFT 研究
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2023-10-05 , DOI: 10.1021/acs.jpca.3c04981
Liudmyla K Sviatenko ₁ , Leonid Gorb _{2,

3} , Jerzy Leszczynski ₁

Affiliation

羟基自由基是水生环境在阳光照射下产生的重要活性氧。由于其高氧化能力，许多有机污染物在遇到羟基自由基时可能会被分解。NTO（5-硝基-1,2,4-三唑-3-酮）是一种用于军事应用的含能材料，由于其良好的水溶性，可能会释放到环境中并溶解在地表水和地下水中。通过 PCM/M06-2 X /6-311++G(d,p)的计算研究，详细研究了羟基自由基引起的 NTO 在水中分解的可能机制，作为 NTO 环境降解的途径之一。等级。人们发现NTO的分解是一个多步骤过程，可能从羟基自由基加成到C=N双键的碳原子上开始，随后释放出亚硝酸自由基。形成的中间体经历一系列化学转化，包括羟基自由基与碳原子的连接、氢向羟基自由基的转移、异构化和键断裂，产生低重量的无机化合物，如氨、氮气、亚硝酸。酸、硝酸和氧化碳(IV)。与其中性形式相比，NTO 的阴离子形式更容易与羟基自由基相互作用。计算的活化能和所研究过程的高能能性支持羟基自由基对环境中 NTO 矿化的显着贡献。

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Role of Hydroxyl Radical in Degradation of NTO: DFT Study

Hydroxyl radicals are important reactive oxygen species produced in the aquatic environment under sunlight irradiation. Many organic pollutants may be decomposed as they encounter hydroxyl radicals, due to their high oxidative ability. NTO (5-nitro-1,2,4-triazol-3-one), an energetic material used in military applications, may be released to the environment and dissolved in surface water and groundwater due to its good water solubility. A detailed investigation of the possible mechanism for NTO decomposition in water induced by hydroxyl radical as one of the pathways for NTO environmental degradation was performed by computational study at the PCM/M06-2X/6-311++G(d,p) level. Decomposition of NTO was found to be a multistep process that may begin with an addition of hydroxyl radical to the carbon atom of C═N double bond and consequent release of a nitrite radical. The formed intermediate undergoes a series of chemical transformations that include the attachments of hydroxyl radical to carbon atoms, the transfer of hydrogen to hydroxyl radical, isomerization, and bond cleavage, leading to low-weight inorganic compounds, such as ammonia, nitrogen gas, nitrous acid, nitric acid, and carbon(IV) oxide. The anionic form of NTO is more reactive toward interaction with the hydroxyl radical as compared with its neutral form. Calculated activation energies and high exergonicity of the studied process support the significant contribution of the hydroxyl radical to NTO mineralization in environment.

更新日期：2023-10-05

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