Computational Study of Carbon Dioxide Capture by Tertiary Amines

The reaction mechanisms and corresponding structure‐activity relationships of tertiary amines with respect to CO2 capture have been investigated using density functional theory (DFT) calculations. The reaction mechanism for CO2 capture via base‐catalyzed hydration to form bicarbonate is proposed to proceed in a single step involving proton transfer and the formation of a carbon‐oxygen bond. Based on the height of the reaction barriers, we suggest that amines containing side chains with the ethyl group, along with a single hydroxyl group, and cyclic structures, are especially active for CO2 capture. The activation barrier is shown to be a descriptor for predicting the experimental CO2 loading values. To enhance the prediction accuracy for CO2 loading, we employ the sure‐independence screening and sparsifying operator (SISSO) method, which can scan a large pool of mathematical terms stemming from combining DFT‐derived descriptors to select the superior ones. Thus, we can predict the CO2 loading with acceptable accuracy from the obtained mathematical expression. Since the computational workload of applying this expression is negligible, this facilitates high‐throughput screening and accelerates the design of tertiary amines for CO2 capture.