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一氧化碳和甲醇在水和硝酸水合物冰中的光化学:NEXAFS 研究。

Photochemistry of carbon monoxide and methanol in water and nitric acid hydrate ices: A NEXAFS study.

机构信息

Laboratoire de Chimie-Physique, Matière et Rayonnement, Université Pierre-et-Marie Curie (UPMC-Univ Paris 06) and CNRS (UMR 7614), 11 rue Pierre-et-Marie-Curie, 75231 PARIS CEDEX 05, France.

出版信息

Phys Chem Chem Phys. 2010 Sep 28;12(36):10865-70. doi: 10.1039/c0cp00229a. Epub 2010 Jul 26.

Abstract

Soft X-ray induced chemistry of H(2)O, CO and CH(3)OH and the effects of the water and nitric acid hydrate (HNO(3).1.65H(2)O) matrix on the photochemistry of CO and CH(3)OH have been investigated using NEXAFS spectroscopy. For pure H(2)O, CO and CH(3)OH ices, we show that the destruction rates are strongly limited by back reactions, leading to strikingly high survival rates of these molecules upon the harsh irradiation conditions to which they are submitted. We also evidence the interplay between the photochemical reactions of CO and CH(3)OH and those of the matrix. The OH and O radicals released by the photolysis of H(2)O and HNO(3) react with the CO and CH(3)OH and their fragments, considerably reducing the survival rates compared to pure CO and pure CH(3)OH ices, especially in presence of nitric acid, and dramatically enhancing the formation of CO(2) at the expense of CO. Because NEXAFS spectroscopy allows identifying which reactions are important among those possible, it emerges a simple picture of the photochemical routes of CO and CH(3)OH in the H(2)O and HNO(3)/H(2)O environments.

摘要

利用近边 X 射线吸收精细结构光谱技术研究了软 X 射线诱导的 H2O、CO 和 CH3OH 的化学反应,以及水和硝酸水合物(HNO3·1.65H2O)基质对 CO 和 CH3OH 光化学的影响。对于纯 H2O、CO 和 CH3OH 冰,我们表明破坏速率受到强烈的反向反应限制,导致这些分子在苛刻的辐照条件下具有很高的存活率。我们还证明了 CO 和 CH3OH 的光化学反应与基质之间的相互作用。H2O 和 HNO3 光解释放的 OH 和 O 自由基与 CO 和 CH3OH 及其碎片反应,大大降低了它们的存活率,与纯 CO 和纯 CH3OH 冰相比,尤其是在存在硝酸的情况下,显著提高了 CO2 的形成速度,同时牺牲了 CO。由于近边 X 射线吸收精细结构光谱技术能够识别出可能发生的重要反应,因此在 H2O 和 HNO3/H2O 环境中,CO 和 CH3OH 的光化学途径呈现出一种简单的图景。

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