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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Computational study of CO2 reduction by amines
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Computational study of CO2 reduction by amines

机译：胺类化合物减少二氧化碳排放的计算研究

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Calculations at the MP2/aug-cc-pVDZ//MPWB1K/aug-cc-pVDZ level are reported for the reduction of CO2 by aminesprimarily triethylamine. A polarizable continuum model is used to represent acetonitrile solvent for the reaction. Starting from a photochemically generated radical ion pair state, the mechanism of reduction is deduced to be one in which the CO2 center dot- begins to use one of its oxygens to abstract a hydrogen from an alpha carbon of the amine radical cation. During this event, and before the transition state for H transfer is reached, the system encounters a surface crossing, which provides pathways for unproductive back electron transfer and for productive reduction, with the latter involving attachment of the hydrogen to the carbon of CO2. The result of the reduction is a closed-shell iminium formate ion pair, which completes the reaction by proton transfer between the ions, to give an eneamine and formic acid. On the basis of the calculations, approaches for improving the efficiency of the reduction and increasing the wavelength of the light used to drive the reaction are discussed. One of these modifications involves the use of a bicyclic amine as reductant.
机译：报导了在MP2 / aug-cc-pVDZ // MPWB1K / aug-cc-pVDZ水平上的计算，表明胺主要是三乙胺对CO2的还原作用。使用可极化的连续体模型表示反应的乙腈溶剂。从光化学产生的自由基离子对状态开始，还原机理被推论为其中CO2中心点开始使用其氧之一从胺自由基阳离子的α碳中提取氢的机理。在此事件期间，并且在达到H转移的过渡状态之前，系统遇到表面交叉，这为非生产性的反向电子转移和生产性还原提供了途径，后者涉及将氢附着到CO2的碳上。还原的结果是闭壳的甲酸亚氨基甲酸亚铵离子对，它通过离子之间的质子转移完成反应，生成烯胺和甲酸。在计算的基础上，讨论了用于提高还原效率和增加用于驱动反应的光的波长的方法。这些修饰之一涉及使用双环胺作为还原剂。

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