Reactivity of Criegee Intermediates toward Carbon Dioxide

被引:26
作者
Lin, Yen-Hsiu [1 ,2 ]
Takahashi, Kaito [1 ]
Lin, Jim Jr-Min Jr [1 ,2 ]
机构
[1] Acad Sinica, Inst Atom & Mol Sci, Taipei 10617, Taiwan
[2] Natl Taiwan Univ, Dept Chem, Taipei 10617, Taiwan
来源
JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2018年 / 9卷 / 01期
关键词
CONFORMER-DEPENDENT REACTIVITY; MOLECULAR-ORBITAL METHODS; WAVE-FUNCTIONS; ATMOSPHERIC IMPLICATIONS; TEMPERATURE-DEPENDENCE; RATE COEFFICIENTS; WATER-VAPOR; BASIS-SETS; KINETICS; CH2OO;
D O I
10.1021/acs.jpclett.7b03154
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Recent theoretical work by Kumar and Francisco suggested that the high reactivity of Criegee intermediates (CIs) could be utilized for designing efficient carbon capture technologies. Because the anti-CH3CHOO + CO2 reaction has the lowest barrier in their study, we chose to investigate it experimentally. We probed anti-CH3CHOO with its strong UV absorption at 365 nm and measured the rate coefficient to be <= 2 x 10(-17) cm(3) molecule(-1) s(-1) at 298 K, which is consistent with our theoretical value of 2.1 x 10(-17) cm(3) molecule(-1) s(-1) at the QCISD(T)/CBS//B3LYP/6-311+G(2d,2p) level but inconsistent with their results obtained at the M06-2X/aug-cc-pVTZ level, which tends to underestimate the barrier heights. The experimental result indicates that the reaction of a Criegee intermediate with atmospheric CO2 (400 ppmv) would be inefficient (k(eff) < 0.2 s(-1)) and cannot compete with other decay processes of Criegee intermediates like reactions with water vapor (similar to 10(3) s(-1)) or thermal decomposition (similar to 10(2) s(-1)).
引用
收藏
页码:184 / 188
页数:5
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