| 基于密度泛函理论对等离子体中H/CO2相互作用的第一性原理研究 |
| First-Principles Calculation of H/CO2 Interaction in Plasma: A Density Functional Theory-Based Study |
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| 摘要: 深入理解辐照条件下氢同位素与CO2反应的微观机制，可为聚变堆氘氚燃料循环工艺的优化设计提供数据支撑。基于此，采用第一性原理计算研究了等离子体放电条件下H2和CO2的微观反应机制，研究了不同温度和氢同位素效应对反应过程的影响。通过内禀反应坐标（IRC）算法结合反应过渡态获得4条初始反应路径，并对比研究了生成产物CH4及CH3OH的2条路径在热力学上的容易程度，以及不同氢同位素对各个反应的影响。研究发现，氚的自发衰变或等离子体中的高能电子都会诱导氢同位素与CO2发生反应，形成CO、H2O、CH4及CH3OH等产物；在高能电子诱导CO2的离解后，由4条初始反应路径组成的复杂反应可以自持发生，且该复杂反应中存在2种倾向；升高反应温度对CO2转化为有机物（CH4和CH3OH）具有一定的促进作用。 |
| 关键词: 二氧化碳转化 氢同位素 密度泛函理论 等离子体 反应路径 |
| 基金项目: 表面物理与化学重点实验室稳定支持项目（No.WDZC202103）资助 |
| Abstract: An in-depth understanding of the microscopic mechanism of the reaction of hydrogen isotopes with CO2 under irradiation conditions can provide data support for the optimal design of the deuterium-tritium fuel cycle process for fusion reactors. Based on this, the microscopic reaction mechanism of H2 and CO2 under the condition of plasma discharge was studied by first-principles calculation, and the influences of different temperatures and hydrogen isotope effect on the reaction process were studied. The principal calculation was carried out by the Gaussian 09 software package. The enthalpies and activation energies of these reactions were measured at the level of M06-2X/6-311++G (3d2f, 3p2d). Four initial reaction paths are obtained by using the intrinsic reaction coordinate (IRC) algorithm and finding the transition state of the combined reaction. The thermodynamic easiness of the two pathways to produce CH4 and CH3OH and the influence of different hydrogen isotopes on each reaction were compared and studied. It is found that the spontaneous decay of tritium or the high-energy electrons in the plasma will induce hydrogen isotopes to react with CO2 to form products such as CO, H2O, CH4, and CH3OH; after the high-energy electrons induce the dissociation of CO2, there are four initial reaction paths. Complex reactions can occur on their own, and there are two tendencies to this complex reaction. Raising the reaction temperature has a certain promoting effect on the conversion of CO2 into organic matter (CH4 and CH3OH). |
| Keywords: CO2 conversion hydrogen isotope density functional theory plasma reaction path |
| 投稿时间：2021-12-14 修订日期：2022-04-23 |
| 摘要点击次数: 1204 |
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| 王雪峰,沈崇雨,吴吉良,叶小球.基于密度泛函理论对等离子体中H/CO2相互作用的第一性原理研究[J].无机化学学报,2022,38(8):1470-1476. |
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