三烷基锍阳离子有望捕获二氧化碳：新型二氧化碳清除剂的硅基证据
The Trialkylsulfonium Cation Holds Promise to Capture Carbon Dioxide: In-Silico Evidence Toward a Novel Carbon Dioxide Scavenger
AI总结：
本研究首次提出三烷基锍非质子离子液体可作为高容量CO₂清除剂，通过杂化密度泛函理论验证其化学吸附各阶段的反应可行性，为新型碳捕获材料设计提供理论依据。
摘要：
地球大气中的二氧化碳（CO₂）浓度与全球变暖这一严峻问题密切相关。本文首次引入三烷基锍非质子离子液体（ILs）作为一类看似高容量的CO₂清除剂。我们通过杂化密度泛函理论记录的反应曲线，论证了这种新型吸附剂的可行性。\n我们探究了构成CO₂化学吸附的所有阶段，例如乙基二甲基锍S211阳离子去质子化、S211叶立德在α-亚甲基处的羧化反应，以及非质子阴离子的羧酰胺化反应。S211叶立德的生成反应在热化学上是禁阻的，但其能量成本是可承受的：能量成本范围从S211吲唑盐的极低值14 kJ/mol到S211 1,2,4-三唑盐的中等值50 kJ/mol。锍基阳离子去质子化对应的能垒范围为苯并咪唑盐的39 kJ/mol到1,2,4-三唑盐的+60 kJ/mol。\n叶立德中间体形成过程中的能量损失，被后续的锍叶立德羧化反应大幅补偿。该能量增益与杂环非质子阴离子（AHA）的性质弱相关，对于所研究的不同离子物种，增益为99至110 kJ/mol。AHA还凭借其氮位点，通过羧酰胺化途径参与CO₂捕获。热化学上最有利的氨基甲酸酯由S211-吲唑盐生成，能量为68 kJ/mol。与这些反应相关的空间位阻和共价能垒处于热运动能的量级，而AHA的特定化学结构仅产生微小差异。我们从部分原子电荷、几何特征、空间位阻、虚振动频率及相关描述符的角度，对反应能量曲线进行了解释。
英文摘要：
The concentration of carbon dioxide (CO2) in the Earth atmosphere is linked to the acute problem of global warming. For the first time, we herein introduce trialkylsulfonium aprotic ionic liquids (ILs) as a group of seemingly highly capacitive CO2 scavengers. We advocate the viability of the new sorbents by the reaction profiles recorded by means of hybrid density functional theory. All stages constituting CO2 chemisorption, such as the ethyldimethylsulfonium S211-cation deprotonation, S211-ylide carboxylation at the alpha-methylene group, and aprotic anion carboxamidation have been explored. The S211-ylide formation reaction is thermochemically forbidden but its cost is affordable. The energetic cost ranges from a tiny number of 14 kJ/mol for S211 indazolide to a mediocre value of 50 kJ/mol for S211 1,2,4-triazolide. The barriers corresponding to the sulfonium-based cation deprotonation range from 39 kJ/mol for benzimidazolide to +60 kJ/mol for 1,2,4-triazolide. The energy loss during the ylide intermediate formation is strongly compensated for by the subsequent sulfonium ylide carboxylation. The energetic gain is weakly dependent on the nature of the heterocyclic aprotic anion being 99 to 110 kJ/mol for different ionic species studied. The AHAs additionally participate in CO2 capture following the route of carboxamidation thanks to their nitrogen sites. The most thermochemically favorable carbamate forms out of S211-indazolide, 68 kJ/mol. The steric and covalent barriers associated with these reactions are of the order of thermal motion energy, whereas a specific chemical structure of AHA engenders marginal differences. The rationalization of the energy reaction profiles is given in terms of partial atomic charges, geometrical peculiarities, steric barriers, imaginary vibrational frequencies, and related descriptors.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
