·OH自由基引发的1,1,2,3-四氟丙烯(CF2=CF–CH2F)的对流层氧化及其产物自由基的空气降解,ACS Earth and Space Chemistry

当前位置： X-MOL 学术 › ACS Earth Space Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

·OH自由基引发的1,1,2,3-四氟丙烯(CF2=CF–CH2F)的对流层氧化及其产物自由基的空气降解
ACS Earth and Space Chemistry ( IF 2.9 ) Pub Date : 2023-01-15 , DOI: 10.1021/acsearthspacechem.2c00353
Udeshna Priya Kakati ₁ , Dikshita Dowerah ₂ , Ramesh Chandra Deka ₂ , Nand Kishor Gour ₂ , Subrata Paul ₁

Affiliation

在大规模应用之前，了解 1,1,2,3-四氟丙烯 (CF ₂ =CF–CH ₂ F)的对流层化学和环境影响至关重要。因此，在目前的工作中，我们进行了^· OH 自由基引发的 CF ₂ =CF–CH ₂ F 氧化的量子化学计算。首先，标题反应的所有反应物种都在 M06-2X/6 处进行了优化-311+G(d,p) 理论水平，然后在具有相同基组的 CCSD(T) 水平上细化能量。相对能量和热化学估计表明^{· OH自由基与CF}₂双键碳原子的加成反应=CF–CH ₂^{F 在能量和热力学上比·} OH自由基的直接夺氢反应更占主导地位。速率常数和支化比分析也表明^· OH-加成反应优于 H-提取反应。根据变分过渡态理论计算，该反应在 298.15 K 下的估计总速率常数为 9.27 × 10 ^–13 cm ³ molecule ^–1 s ^{–1 。}_{CF 2} = CF–CH ₂ F的大气寿命计算为12.5 天关于^· OH 反应。辐射效率计算为 0.016 W m ^–2 ppb^–1，并且 CF ₂ =CF–CH ₂ F 在不同时间范围内的全球变暖潜能值非常低。此外，光化学臭氧产生潜力估计为 5.55。最后，使用相同的量子化学方法研究了在存在 NO 自由基的情况下，^· OH 加成产物自由基的空气降解。从这项降解研究中，我们观察到 CF ₂ (OH)COF、FCOCH ₂ F、FCFO、FCOOH 和^· CH ₂ F 作为最终产物形成。

"点击查看英文标题和摘要"

Tropospheric Oxidation of 1,1,2,3-Tetrafluoropropene (CF2=CF–CH2F) Initiated by ·OH Radical and Aerial Degradation of Its Product Radicals

It is essential to understand the tropospheric chemistry and environmental impact of 1,1,2,3-tetrafluoropropene (CF₂=CF–CH₂F) before its wide-scale applications. So, in this present work, we have performed the quantum chemical calculations of the ^·OH radical initiated oxidation of CF₂=CF–CH₂F. First, all the reaction species of the title reaction are optimized at the M06-2X/6-311+G(d,p) level of theory and then the energies are refined at the CCSD(T) level with the same basis set. The relative energy and thermochemistry estimations indicate that the addition reactions of the ^·OH radical to the carbon atoms of the double bond of CF₂=CF–CH₂F are energetically and thermodynamically more dominant rather than the direct H-abstraction reactions by the ^·OH radical. The rate constant and branching ratio analysis also indicate the favorability of the ^·OH-addition reactions over the H-abstraction reactions. The estimated overall rate constant at 298.15 K for this reaction is found to be 9.27 × 10^–13 cm³ molecule^–1 s^–1 computed by variational transition state theory. The atmospheric lifetime of CF₂ = CF–CH₂F is calculated as 12.5 days with respect to ^·OH reaction. The radiative efficiency is calculated as 0.016 W m^–2 ppb^–1, and global warming potentials of CF₂=CF–CH₂F for the different time horizons are significantly low. Further, photochemical ozone creation potential is estimated as 5.55. Finally, aerial degradation of the ^·OH-addition product radicals was studied in the presence of the NO radical using the same quantum chemical method. From this degradation study, we have observed that CF₂(OH)COF, FCOCH₂F, FCFO, FCOOH, and ^·CH₂F are formed as end products.

更新日期：2023-01-15

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南