Characterization of chemisorption products from CO2 and amine bearing polymers via solid-state NMR
EMSL Project ID
48753
Abstract
The objective of this proposed work is to characterize the chemisorption products of CO2 interacting with solid-supported amine materials. The aim is to use these materials to capture CO2 from flue gasses, reducing the output of CO2 into the atmosphere, and thus, minimize its effect on the global environment. The reactions of CO2 and amines in liquid-phase are well known, with possible products including carbamate and bicarbonate. Preliminary studies of these systems with 13C{1H} CPMAS NMR have a single resonance centered at 163.5 ppm with a fwhm of 3.5 ppm. This makes the assignment of the peak problematic as the peak could be comprised of carbamate, bicarbonate, or a mixture of chemisorption products. This proposal is to take advantage of the low-field, 100 MHz (2.35 T) instrument for further 13C{1H} CPMAS NMR studies. In order to distinguish the chemisorption product of these CO2 and amine reactions, we propose to exploit the differences in coordination environment of the carbonyl carbon in bicarbonate and carbamate. The key difference is that carbamate has a carbon-nitrogen bond making it possible to use the 13C-14N dipolar coupling to discriminate carbamate from bicarbonate. At low magnetic fields, the 13C-14N dipolar coupling is not averaged to zero and instead splits the 13C resonance into two characteristic peaks. Therefore, at low magnetic fields, the carbamate resonance will appear as two peaks while bicarbonate will only have a single peak. The proposed work will study samples with a single type of amine (primary, secondary, tertiary) and samples with different concentrations of amine sites within the support structure. By controlling these variables, their effects on the chemisorption product will be identified. This work, characterizing the products of CO2 and amines reactions, will expose details of the chemical mechanisms involved in chemisorption. The improved understanding of the adsorption process will aid in the production of new technologies utilized in the capture of carbon dioxide.
Project Details
Project type
Exploratory Research
Start Date
2015-03-09
End Date
2015-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Hammann B.A., D.A. Marsh, Z.L. Ma, S.R. Wood, M.E. West, D.W. Johnson, and S.E. Hayes. 2016. "Synthetic Routes to a Nanoscale Inorganic Cluster [Ga13(µ3-OH)6 (µ2-OH)18(H2O)](NO3)15 Evaluated by Solid-State 71Ga NMR." Journal of Solid State Chemistry 242. doi:10.1016/j.jssc.2016.02.043