DFT 研究 BF 阴离子存在时常见环状碳酸盐的氧化机制。
DFT Study on the Oxidation Mechanism of Common Cyclic Carbonates in the Presence of BF Anions.
机构信息
Institute of Batteries, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China.
Engineering Research Center of MTEES (Ministry of Education), Research Center of BMET (Guangdong Province), Engineering Laboratory of OFMHEB (Guangdong Province), Key Laboratory of ETESPG (GHEI), and Innovative Platform for ITBMD (Guangzhou Municipality), School of Chemistry, South China Normal University, Guangzhou 510006, China.
出版信息
J Phys Chem A. 2023 May 11;127(18):3958-3965. doi: 10.1021/acs.jpca.2c07827. Epub 2023 Apr 28.
Oxidative decomposition reactions of common cyclic carbonates in the presence of BF anions were investigated using density functional theory. A polarized continuum model was utilized to model solvent effects in the oxidation of ethylene carbonate (EC) and propylene carbonate (PC) clusters. We have found that the presence of BF significantly reduces EC and PC oxidation stability, from 7.11 to 6.17 and from 7.10 to 6.06 V (vs Li/Li), respectively. The sequence of EC and PC oxidative decomposition paths and the oxidative products were affected by the BF anion. The decomposition products of the oxidized EC-BF contained CO, vinyl alcohol, and acetaldehyde, while the decomposition products of the oxidized PC-BF contained CO, acetone, and propanal, in agreement with the previous experimental studies. The oxidative decomposition reactions for PC-BF are compared with those for the isolated PC, PC PC-ClO, and PC-PF.
采用密度泛函理论研究了 BF 阴离子存在下常见环状碳酸酯的氧化分解反应。利用极化连续模型模拟了氧化乙烯碳酸酯（EC）和碳酸丙烯酯（PC）团簇时的溶剂效应。我们发现 BF 的存在显著降低了 EC 和 PC 的氧化稳定性，分别从 7.11 伏（相对于 Li/Li）降至 6.17 伏和从 7.10 伏降至 6.06 伏。BF 阴离子影响 EC 和 PC 氧化分解路径的顺序和氧化产物。氧化 EC-BF 的分解产物包括 CO、乙烯醇和乙醛，而氧化 PC-BF 的分解产物包括 CO、丙酮和丙醛，这与之前的实验研究一致。还比较了 PC-BF 的氧化分解反应与孤立的 PC、PC-PC-ClO 和 PC-PF 的氧化分解反应。
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