In situ monitoring of CO2$$ {}_2 $$ sorption on polyethylenimine dynamics through broadband dielectric spectroscopy

Chemical reactions between carbon dioxide (CO) and amine have been extensively characterized, however, their influence on the dynamics of polyamines remains largely unexplored. In this work, we compare the dynamics of polyethylenimine (PEI) before and after CO absorption through broadband dielectric spectroscopy (BDS). The molecular processes of bulk PEI are very different from those of thin film PEI, highlighting an interesting interface and nano‐confinement effect. Detailed analyses show CO absorption slows down the PEI dynamics, which is consistent with an elevated glass transition temperature of PEI upon CO absorption from differential scanning calorimetry measurements. Further in situ kinetic measurements demonstrate nonmonotonic changes in relaxation times or dielectric amplitudes of some relaxation processes during CO sorption or desorption, suggesting an intriguing interplay between CO chemisorption and the dynamics of PEI. These results demonstrate that BDS is a powerful platform to resolve the temporal dynamics changes of polyamines for CO capture.