Hydrotrioxide (ROOOH) formation in the atmosphere
Hydrotrioxide (ROOOH) formation in the atmosphere
复制标题
DOI：
10.1126/science.abn6012
复制
发表时间：
2022-05-27
期刊：
影响因子：
56.9
通讯作者：
Kjaergaard, Henrik G.
中科院分区：
文献类型：
--
作者：
Berndt, Torsten;Chen, Jing;Kjaergaard, Henrik G.
已知有机氢三氧化物（ROOOH）是有机合成中使用的强氧化剂。此前，有人推测它们是在大气中通过有机过氧自由基（RO2）与羟基自由基（OH）的气相反应形成的。在这里，我们报告了从几个与大气相关的 RO2 自由基中直接观察到 ROOOH 形成的情况。动力学分析证实了 RO2 + OH 快速反应形成 ROOOH，速率系数接近碰撞极限。对于 OH 引发的异戊二烯降解，全局模型预测摩尔三氧化二氢形成产率高达 1%，这意味着每年大约形成 1000 万吨 ROOOH。 ROOOH 的大气寿命估计为几分钟到几小时。三氧化氢代表了大气中以前被忽略的一类物质，其影响需要检查。
Organic hydrotrioxides (ROOOH) are known to be strong oxidants used in organic synthesis. Previously, it has been speculated that they are formed in the atmosphere through the gas-phase reaction of organic peroxy radicals (RO2) with hydroxyl radicals (OH). Here, we report direct observation of ROOOH formation from several atmospherically relevant RO2 radicals. Kinetic analysis confirmed rapid RO2 + OH reactions forming ROOOH, with rate coefficients close to the collision limit. For the OH-initiated degradation of isoprene, global modeling predicts molar hydrotrioxide formation yields of up to 1%, which represents an annual ROOOH formation of about 10 million metric tons. The atmospheric lifetime of ROOOH is estimated to be minutes to hours. Hydrotrioxides represent a previously omitted substance class in the atmosphere, the impact of which needs to be examined.