文献类型：期刊文献

英文题名：1-Butyl-1-Methylpyrrolidinium-Based Ionic Liquids for Integrated Co2 Absorption and Transformation into Dimethyl Carbonate

作者：Chen, Lifang[1,2]; Zhang, Wanting[2]; Ruan, Jiawei[2]; Wu, Xinzi[2]; Liu, Qian[2]; Xie, Kunchi[2]; Qi, Zhiwen[1,2]

机构：[1] Max Planck Partner Group, Germany; [2] State Key laboratory of Chemical Engineering and Low-carbon Technology, School of Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China

年份：2025

外文期刊名：SSRN

收录：EI(收录号：20250347709)

语种：英文

外文关键词：Carbon capture - Carbon capture and storage - Carbon capture and utilization - Carbon dioxide - Carbonation - Chemical activation - Chemical bonds - Density functional theory - Extraction - Negative ions - Phase transitions - Reaction intermediates

摘要：The transformation of captured CO2 into highly-valued dimethyl carbonate (DMC) is a promising approach for CO2 capture and utilization. However, the direct synthesis of DMC from CO2 and methanol is limitted by high activation barrier derived from inert CO2 and thermodynamic equilibrium constraints. Herein, three 1-butyl-1-methylpyrrolidinium (BMP)-based ILs with polar pyrrole, pyrazole, and 1,2,4-triazole (Tz) azole anions were designed to integrate CO2 absorption and transformation into DMC. [BMP][Tz] exhibits a relatively high CO2 uptake capacity of 0.6 mol·molIL?1 and DMC yield reaches 12.2% under mild reaction conditions of atmospheric temperature and pressure in 12 h. The reaction equilibrium thermodynamic model reveals that [BMP][Tz] illustrates dual 1:1 and 2:1 CO2 absorption mechanisms. Density functional theory calculations verify that [BMP][Tz] with increased basicity of azole anions promotes critical bond activation (particular C?O and O?H bonds), thereby enhancing catalytic efficiency. The reaction mechanism is clarified by intermediates and transition state, and [BMP][Tz] can efficiently decrease the energy barrier of the rate-controlled step, which involves the insertion of CH3O? into CH3OCOO? species. Furthermore, polarity-induced phase separation of DMC from the IL phase to solvent phase favors DMC generation by breaking through the reaction equilibrium. The integration of CO2 absorption-reaction-extraction based on basic and polar ILs, provides a promising approach for CO2 capture and utilization. ? 2025, The Authors. All rights reserved.