First-Principles Study on the Mechanism of Greenhouse Gas Generation in Aluminum Electrolysis
First-Principles Study on the Mechanism of Greenhouse Gas Generation in Aluminum Electrolysis
复制标题
铝电解温室气体产生机理的第一性原理研究
作者：
孙珂娜;李劼;张红亮;李天爽;李家琦
铝电解行业排放的温室气体给环境保护带来了巨大挑战。针对这一问题，了解电解过程中温室气体的微产生机制对于源头抑制具有重要意义。基于第一性原理计算方法，通过研究冰晶石氧化铝熔盐中氧、氟络合阴离子（简称[O]2−、[F]−）在阳极表面的吸附行为，得到了正常电解过程中CO、CO2和COF2的生成路径。计算结果表明，O和F原子更倾向于吸附在模型A的桥位1处，吸附能为-4.82 eV和-3.33 eV。在[O]2−优先放电阶段，路径3是最有可能产生CO2的路径，而在[O]2−、[F]−共同放电阶段，路径3是最有可能产生COF2的路径。据推测，COF2在高温下的热分解应解释低浓度CF4的生成，即所谓的非阳极效应PFC（NAE-PFC）。并通过实验验证了计算结果，揭示了C、O、F的成键信息，与第一性原理计算的结果吻合良好。
Greenhouse gases emitted by the aluminum electrolysis industry have brought great challenges to environmental protection. To address this problem, understanding the micro-generation mechanism of greenhouse gases in the electrolysis process is of great significance to their source suppression. Based on the first principles calculation method, the formation paths of CO, CO2 and COF2 during normal electrolysis were obtained by studying the adsorption behavior of oxygen and fluorine complex anions (short for [O]2−, [F]−) on the anode surface in cryolite alumina molten salt. The calculation results indicate that the O and F atoms prefer to adsorb at bridge site 1 of Model A, with the adsorption energies of −4.82 eV and −3.33 eV. In the [O]2− priority discharge stage, Path 3 is the most likely path for CO2 generation, while in the [O]2−, [F]− co-discharge stage, Path 3 is the most likely path for COF2 generation. It is deduced that the thermal decomposition of COF2 at high temperature should account for the generation of CF4 with a low concentration of the so-called non-anode effect PFC (NAE-PFC). Experiments were also conducted to verify the calculation by disclosing the bonding information of C, O and F, which are in good accordance with the results calculated by the first principle.
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DOI：
10.1007/978-3-319-48160-9_55
发表时间：
2011-05
期刊：
Light Metals
影响因子：
--
作者：
Wangxing Li;Qingyun Zhao;Jian-hong Yang;Shi-lin Qiu;Xiping Chen;J. Marks;C. Bayliss
通讯作者：
Wangxing Li;Qingyun Zhao;Jian-hong Yang;Shi-lin Qiu;Xiping Chen;J. Marks;C. Bayliss
DOI：
10.1007/978-3-319-72284-9_189
发表时间：
2018-03
期刊：
--
影响因子：
--
作者：
O. Kjos;A. Solheim;T. Aarhaug;K. Osen;A. Martínez;Camilla Sommerseth;H. Gudbrandsen;Anne Støre;H. Gaertner
通讯作者：
O. Kjos;A. Solheim;T. Aarhaug;K. Osen;A. Martínez;Camilla Sommerseth;H. Gudbrandsen;Anne Støre;H. Gaertner
影响因子：
2.9
作者：
S. Djokić;B. Conway;T. Belliveau
通讯作者：
S. Djokić;B. Conway;T. Belliveau
影响因子：
2.4
作者：
H. Vogel;Benedikt Flerus;Felix Stoffner;B. Friedrich
通讯作者：
H. Vogel;Benedikt Flerus;Felix Stoffner;B. Friedrich
DOI：
10.1007/s11431-009-0165-6
发表时间：
2009-08
期刊：
Science in China Series E: Technological Sciences
影响因子：
--
作者：
F. Gao;Z. Nie;Zhihong Wang;Hongmei Li;X. Gong;T. Zuo
通讯作者：
F. Gao;Z. Nie;Zhihong Wang;Hongmei Li;X. Gong;T. Zuo