Carbon dioxide capture in 2,2'-iminodiethanol aqueous solution from ab initio molecular dynamics simulations.

Abstract

The reaction of carbon dioxide (CO2) with aqueous 2,2'-iminodiethanol (trivial name is diethanolamine: DEA) has been investigated using both blue moon ensemble and metadynamics approaches combined with ab initio molecular dynamics (AIMD) simulations. A spontaneous direct proton transfer from DEA zwitterion (DEAZW) to DEA but not to H2O has been observed in straightforward AIMD simulation in the time scale of ps. The ab initio free-energy calculations reproduced the overall free-energy difference, predicting the ionic products DEA carbamate ion (DEAC) and the protonated DEA (DEAH). The computed free-energy barrier for the first reaction step, which is the CO2 binding (48 kJ mol-1), is found to agree reasonably well with the available experimental data (52-56 kJ mol-1). By contrast, the barriers for the next step, the deprotonation of zwitterion realized either via reaction with DEA or H2O, are underestimated by 25-35 kJ mol-1 compared to the experimental reference. A part of this error is attributed to the neglected reversible work needed to bring two reactants together, which might significantly contribute to the free-energy of activation of bimolecular reactions in a dilute solution. The computed free-energy profile is compared with our results [Y. Kubota et al., J. Chem. Phys. 146, 094303 (2017)] for the same reaction in 2-aminoethanol (trivial name is monoethanolamine: MEA).