Direct dioxygen evolution in collisions of carbon dioxide with surfaces
Direct dioxygen evolution in collisions of carbon dioxide with surfaces
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DOI：
10.1038/s41467-019-10342-6
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发表时间：
2019-05
影响因子：
16.6
通讯作者：
Yunxi Yao;Philip Shushkov;Thomas F. Miller;K. Giapis
中科院分区：
文献类型：
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作者：
Yunxi Yao;Philip Shushkov;Thomas F. Miller;K. Giapis
分子内二氧化碳到分子氧的转化是一种外来反应，即使用极端的光学或电子激发手段也很少观察到。在这里，我们表明，当co2离子在高温入射能量下从固体表面散射时，这种反应很容易发生在两步连续碰撞过程中。产生的O2通过从表面的电荷转移优先电离，而不是主要的原子氧产物，从而直接检测O2+和O2−。碰撞动力学的第一性原理模拟表明，二氧化碳的产生是通过强弯曲的二氧化碳构型进行的，而不需要访问其他中间产物。弯曲的co2提供了动态途径，使co2对称解离为C+ o2，根据分子取向，计算出的产率为1%至2%。这种意想不到的碰撞诱导的单个二氧化碳分子的转化为在天体物理环境中产生二氧化碳提供了一条可行的途径，并可能启发等离子体驱动的电和光催化策略，用于陆地上的二氧化碳还原。
The intramolecular conversion of CO2to molecular oxygen is an exotic reaction, rarely observed even with extreme optical or electronic excitation means. Here we show that this reaction occurs readily when CO2ions scatter from solid surfaces in a two-step sequential collision process at hyperthermal incidence energies. The produced O2is preferentially ionized by charge transfer from the surface over the predominant atomic oxygen product, leading to direct detection of both O2+and O2−. First-principles simulations of the collisional dynamics reveal that O2production proceeds via strongly-bent CO2configurations, without visiting other intermediates. Bent CO2provides dynamic access to the symmetric dissociation of CO2to C+O2with a calculated yield of 1 to 2% depending on molecular orientation. This unexpected collision-induced transformation of individual CO2molecules provides an accessible pathway for generating O2in astrophysical environments and may inspire plasma-driven electro- and photo-catalytic strategies for terrestrial CO2reduction.