Highly efficient DES-based catalytic systems for carbon dioxide utilization via cycloaddition with epoxide substrates

Abstract

The accumulation of greenhouse gases (GHG) in the atmosphere, with carbon dioxide being the most significant contributor, is a major environmental problem as it impacts significantly on climate change. The development of new catalysts and chemical reactions that incorporate CO2 are needed to reduce its further emission significantly. Deep eutectic solvents (DES) have garnered increasing attention as environmentally friendly catalysts in the cycloaddition of carbon dioxide (CO2) with epoxide substrates to produce cyclic carbonates. Their appeal stems from their facile synthesis, cost-effectiveness, low vapour pressure, and thermal stability. In this study, we present a convenient solvent-free synthesis method for nine deep eutectic solvents (DES), utilizing varying compositions of quaternary amine salts (N,N,N-triethyldodecan-1-aminium hydroxide, [TEA-12][OH]) and quinaldic acid [Q-COOH]. These deep eutectic solvents were thoroughly characterized using several techniques, including FTIR, NMR, DSC, and TGA. Moreover, their efficacy for the solvent-free fixation of CO2 to cyclic carbonates were evaluated. Among the tested compositions, [TEA-12]:[Q-COOH] (0.9:0.1) exhibited the lowest melting point (100.17 °C) and highest catalytic activity, showcasing an optimized Turn-Over Frequency (TOF) of 1466 h−1. This remarkable result represents a significant advancement in the application of DES for CO2 fixation, exceeding the previous highest catalytic activity observed with TBAB:Citric acid (2.5:1) by more than tenfold.