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Title: Spectroscopic Investigation of the Mechanisms Responsible for the Superior Stability of Hybrid Class 1/Class 2 CO 2 Sorbents: A New Class 4 Category

Hybrid Class 1/Class 2 supported amine CO 2 sorbents demonstrate superior performance under practical steam conditions, yet their amine immobilization and stabilization mechanisms are unclear. Uncovering the interactions responsible for the sorbents’ robust features is critical for further improvements and can facilitate practical applications. We employ solid state 29Si CP-MAS and 2-D FSLG 1H– 13C CP HETCOR NMR spectroscopies to probe the overall molecular interactions of aminosilane/silica, polyamine [poly(ethylenimine), PEI]/silica, and hybrid aminosilane/PEI/silica sorbents. A unique, sequential impregnation sorbent preparation method is executed in a diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) setup to decouple amine binding mechanisms at the amine–silica interface from those within bulk amine layers. These mechanisms are correlated with each sorbents’ resistance to accelerated liquid H 2O and TGA steam treatments (H 2O stability) and to oxidative degradation (thermal stability). High percentages of CO 2 capture retained (PCR) and organic content retained (OCR) values after H 2O testing of N-(3-(trimethoxysilyl)propyl)ethylenediamine (TMPED)/PEI and (3-aminopropyl)trimethoxysilane (APTMS)/PEI hybrid sorbents are associated with a synergistic stabilizing effect of the amine species observed during oxidative degradation (thermal gravimetric analysis-differential scanning calorimetry, TGA-DSC). Solid state NMR spectroscopy reveals that the synergistic effect of the TMPED/PEI mixture is manifested by the formation ofmore » hydrogen-bonded PEI–NH 2···NH 2–TMPED and PEI–NH 2···HO–Si/O–Si–O (TMPED, T 2) linkages within the sorbent. DRIFTS further determines that PEI enhances the grafting of TMPED to silica and that PEI is dispersed among a stable network of polymerized TMPED in the bulk, utilizing H-bonded linkages. These findings provide the scientific basis for establishing a Class 4 category for aminosilane/polyamine/silica hybrid sorbents.« less
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [5]
  1. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. AECOM, Oak Ridge, TN (United States)
  3. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
  4. Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemistry
  5. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
Publication Date:
Grant/Contract Number:
CBET-1403239; DE-FE0004000
Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 8; Journal Issue: 20; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Research Org:
Oak Ridge Inst. for Science and Education (ORISE), Oak Ridge, TN (United States); National Energy Technology Lab. (NETL), Pittsburgh, PA, and Morgantown, WV (United States)
Sponsoring Org:
USDOE Office of Fossil Energy (FE); AECOM, Oak Ridge, TN (United States); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; amine sorbent; Class 4; CO2 capture; hybrid; infrared spectroscopy; NMR
OSTI Identifier:
1433612

Wilfong, Walter Christopher, Kail, Brian W., Jones, Christopher W., Pacheco, Carlos, and Gray, McMahan L.. Spectroscopic Investigation of the Mechanisms Responsible for the Superior Stability of Hybrid Class 1/Class 2 CO2 Sorbents: A New Class 4 Category. United States: N. p., Web. doi:10.1021/acsami.6b02062.
Wilfong, Walter Christopher, Kail, Brian W., Jones, Christopher W., Pacheco, Carlos, & Gray, McMahan L.. Spectroscopic Investigation of the Mechanisms Responsible for the Superior Stability of Hybrid Class 1/Class 2 CO2 Sorbents: A New Class 4 Category. United States. doi:10.1021/acsami.6b02062.
Wilfong, Walter Christopher, Kail, Brian W., Jones, Christopher W., Pacheco, Carlos, and Gray, McMahan L.. 2016. "Spectroscopic Investigation of the Mechanisms Responsible for the Superior Stability of Hybrid Class 1/Class 2 CO2 Sorbents: A New Class 4 Category". United States. doi:10.1021/acsami.6b02062. https://www.osti.gov/servlets/purl/1433612.
@article{osti_1433612,
title = {Spectroscopic Investigation of the Mechanisms Responsible for the Superior Stability of Hybrid Class 1/Class 2 CO2 Sorbents: A New Class 4 Category},
author = {Wilfong, Walter Christopher and Kail, Brian W. and Jones, Christopher W. and Pacheco, Carlos and Gray, McMahan L.},
abstractNote = {Hybrid Class 1/Class 2 supported amine CO2 sorbents demonstrate superior performance under practical steam conditions, yet their amine immobilization and stabilization mechanisms are unclear. Uncovering the interactions responsible for the sorbents’ robust features is critical for further improvements and can facilitate practical applications. We employ solid state 29Si CP-MAS and 2-D FSLG 1H–13C CP HETCOR NMR spectroscopies to probe the overall molecular interactions of aminosilane/silica, polyamine [poly(ethylenimine), PEI]/silica, and hybrid aminosilane/PEI/silica sorbents. A unique, sequential impregnation sorbent preparation method is executed in a diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) setup to decouple amine binding mechanisms at the amine–silica interface from those within bulk amine layers. These mechanisms are correlated with each sorbents’ resistance to accelerated liquid H2O and TGA steam treatments (H2O stability) and to oxidative degradation (thermal stability). High percentages of CO2 capture retained (PCR) and organic content retained (OCR) values after H2O testing of N-(3-(trimethoxysilyl)propyl)ethylenediamine (TMPED)/PEI and (3-aminopropyl)trimethoxysilane (APTMS)/PEI hybrid sorbents are associated with a synergistic stabilizing effect of the amine species observed during oxidative degradation (thermal gravimetric analysis-differential scanning calorimetry, TGA-DSC). Solid state NMR spectroscopy reveals that the synergistic effect of the TMPED/PEI mixture is manifested by the formation of hydrogen-bonded PEI–NH2···NH2–TMPED and PEI–NH2···HO–Si/O–Si–O (TMPED, T2) linkages within the sorbent. DRIFTS further determines that PEI enhances the grafting of TMPED to silica and that PEI is dispersed among a stable network of polymerized TMPED in the bulk, utilizing H-bonded linkages. These findings provide the scientific basis for establishing a Class 4 category for aminosilane/polyamine/silica hybrid sorbents.},
doi = {10.1021/acsami.6b02062},
journal = {ACS Applied Materials and Interfaces},
number = 20,
volume = 8,
place = {United States},
year = {2016},
month = {5}
}