Understanding the Ingenious Dual Role-Playing of CO₂ in One-Pot Pressure-Swing Synthesis of Linear Carbonate

Abstract

CO2, as an engaging C1 building block, shines brightly in green conversion; besides, its unique identity as an acidic molecule is worthy of further development. Here, a novel mode of CO2 utilization was explored to play a dual role in the one-pot pressure-swing synthesis of dimethyl carbonate (DMC) over 2-hydroxypyridine anion functionalized poly­(ionic liquid)­s (OPy-PILs), that is, CO2 could act as both a raw material of coupling reaction and an acidic inhibitor of side-reaction. Specifically, OPy-PILs, constructed by free radical copolymerization followed by ion exchange, were applied to the one-pot coupling reaction of CO2, epoxide, and CH3OH. As an efficient heterogeneous catalyst, OPy-PILs could cover basic sites with acidic CO2 during the insertion of activated CO2 into epoxide by intermediate [OPy-CO2 –] so as to reduce the yield of the epoxide alcoholysis side-reaction from 27 to 12%. Moreover, various comparative experiments fully exhibited the high activity and stability of OPy-PILs, and theoretical calculations convincingly explained the dual role-playing of CO2 in a one-pot pressure-swing reaction. This work paves a novel avenue for the deeper exploration of the CO2 utilization potential in the catalytic process.

Ionic-Liquid-Assisted One-Step Construction of Mesoporous Metal–Organic Frameworks

“…When compared to [AEIM]­Cl, the electronegativity of the nitrogen atoms (-NH 2 ) in the cations of Phe-IL and HPy-IL was found to be higher, increasing from −0.763 to −0.726 and −0.749, respectively. The increase in electronegativity enhances the ability of an IL to donate electrons when it participates in coordination . When a ligand’s electronegativity increases, the ability of the ligated atoms to donate electrons is improved.…”

“…The increase in electronegativity enhances the ability of an IL to donate electrons when it participates in coordination. 46 When a ligand's electronegativity increases, the ability of the ligated atoms to donate electrons is improved.…”

Construction of DBU–based Poly (ionic liquid)s for the Conversion of CO2, Glycerol, and Propylene Oxide into Glycerol Carbonate

“…The main weight loss was between 350 °C and 500 °C, which was caused by the decomposition of the polymeric carbon nitride framework. [36]…”

Conjugated and Non‐conjugated Polymers Containing Two‐Electron Redox Dihydrophenazines for Lithium‐Organic Batteries

“…Therefore, its structure shown in Figure 1 is drawn according to similar reported crosslinking polymers via free radical polymerization of two vinyl aromatics. [23] Furthermore, the morphology and particle size of polymers CPP and NCPP were investigated by scanning electron microscopy (SEM). As shown in Figures 2b and S7, conjugated polymer CPP exhibits nanosheet morphologies with a thickness of only � 50 nm, which shortened the anion diffusion channel and facilitate a rapid electrochemical reaction rate.…”