Amidine-Functionalized Poly(2-vinyl-4,4-dimethylazlactone) for Selective and Efficient CO₂ Fixing

Journal Article · Fri Feb 12 00:00:00 EST 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.5b02483· OSTI ID:1286751

Barkakaty, Balaka ^[1]; Browning, Katie L. ^[2]; Sumpter, Bobby ^[1]; Uhrig, David ^[1]; Karpisova, Ivana ^[3]; Harman, Kevin W. ^[1]; Ivanov, Ilia ^[1]; Hensley, Dale K. ^[1]; Messman, Jamie M. ^[1]; Kilbey, S. Michael ^[4]; Lokitz, Bradley S. ^[1]

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1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
2. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering
3. Comenius Univ., Bratislava (Slovakia). Dept. of Nuclear Physics and Biophysics
4. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry

Development of novel polymeric materials capable of efficient CO₂ capture and separation under ambient conditions is crucial for cost-effective and practical industrial applications. Here we report the facile synthesis of a new CO₂-responsive polymer through post-polymerization modification of poly(2 vinyl-4,4-dimethylazlactone) (PVDMA). The reactive pendant azlactone groups of PVDMA are easily modified with 4-(N-methyltetrahydropyrimidine) benzyl alcohol (PBA) without any by-product formation. FTIR and TGA experiments show the new PBA functionalized polymer powder can reversibly capture CO₂ at room temperature and under atmospheric pressure. CO2 capture was selective, showing a high fixing efficiency even with a mixed gas system (20% CO₂, 80% N₂) similar to flue gas. CO₂ release occurred at room temperature and release profiles were investigated as a function of temperature. Density Functional Theory (DFT) calculations coupled with modeling and simulation reveal the presence of two CO₂ binding sites in the PBA functionalized polymer resulting in a two-step CO₂ release at room temperature. Finally, we find that the ease of material preparation, high fixing efficiency, and robust release characteristics suggest that post-polymerization modification may be a useful route to designing new materials for CO₂ capture.

• Research Organization: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
• Grant/Contract Number: AC05-00OR22725; 1133320; SC0012577
• OSTI ID: 1286751
• Journal Information: Macromolecules, Vol. 49, Issue 5; ISSN 0024-9297
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 Capture
Polymer
Solid-state
First Principle
Binding Energy
Kinetic Rate Laws