Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO2 Capture Applications: A Quasielastic Neutron Scattering Study
Abstract
Composite gas sorbents, formed from an active polymer phase and a porous support, are promising materials for the separation of acid gases from a variety of gas streams. Significant changes in sorption performance (capacity, rate, stability etc.) can be achieved by tuning the properties of the polymer and the nature of interactions between polymer and support. We utilize quasielastic neutron scattering (QENS) and coarse-grained molecular dynamics (MD) simulations to characterize the dynamic behavior of the most commonly reported polymer in such materials, poly(ethylenimine) (PEI), both in bulk form and when supported in a mesoporous silica framework. The polymer chain dynamics (rotational and translational diffusion) are characterized using two neutron backscattering spectrometers that have overlapping time scales, ranging from picoseconds to a few nanoseconds. Two modes of motion are detected for the PEI molecule in QENS. At low energy transfers, a “slow process” on the time scale of ~200 ps is found and attributed to jump-mediated, center-of-mass diffusion. Second, a “fast process” at ~20 ps scale is also found and is attributed to a locally confined, jump-diffusion. Characteristic data (time scale and spectral weight) of these processes are compared to those characterized by MD, and reasonable agreement is found. For themore »
- Authors:
-
- Georgia Inst. of Technology, Atlanta, GA (United States); Univ. of Colorado, Boulder, CO (United States)
- Georgia Inst. of Technology and Global Thermostat, LLC, Atlanta, GA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Georgia Inst. of Technology, Atlanta, GA (United States)
- Global Thermostat, LLC, Atlanta, GA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1376591
- Grant/Contract Number:
- AC05-00OR22725; SC0012577; DMR-1508249
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 27; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
Citation Formats
Holewinski, Adam, Sakwa-Novak, Miles A., Carrillo, Jan-Michael Y., Potter, Matthew E., Ellebracht, Nathan, Rother, Gernot, Sumpter, Bobby G., and Jones, Christopher W. Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO2 Capture Applications: A Quasielastic Neutron Scattering Study. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcb.7b04106.
Holewinski, Adam, Sakwa-Novak, Miles A., Carrillo, Jan-Michael Y., Potter, Matthew E., Ellebracht, Nathan, Rother, Gernot, Sumpter, Bobby G., & Jones, Christopher W. Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO2 Capture Applications: A Quasielastic Neutron Scattering Study. United States. https://doi.org/10.1021/acs.jpcb.7b04106
Holewinski, Adam, Sakwa-Novak, Miles A., Carrillo, Jan-Michael Y., Potter, Matthew E., Ellebracht, Nathan, Rother, Gernot, Sumpter, Bobby G., and Jones, Christopher W. Tue .
"Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO2 Capture Applications: A Quasielastic Neutron Scattering Study". United States. https://doi.org/10.1021/acs.jpcb.7b04106. https://www.osti.gov/servlets/purl/1376591.
@article{osti_1376591,
title = {Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO2 Capture Applications: A Quasielastic Neutron Scattering Study},
author = {Holewinski, Adam and Sakwa-Novak, Miles A. and Carrillo, Jan-Michael Y. and Potter, Matthew E. and Ellebracht, Nathan and Rother, Gernot and Sumpter, Bobby G. and Jones, Christopher W.},
abstractNote = {Composite gas sorbents, formed from an active polymer phase and a porous support, are promising materials for the separation of acid gases from a variety of gas streams. Significant changes in sorption performance (capacity, rate, stability etc.) can be achieved by tuning the properties of the polymer and the nature of interactions between polymer and support. We utilize quasielastic neutron scattering (QENS) and coarse-grained molecular dynamics (MD) simulations to characterize the dynamic behavior of the most commonly reported polymer in such materials, poly(ethylenimine) (PEI), both in bulk form and when supported in a mesoporous silica framework. The polymer chain dynamics (rotational and translational diffusion) are characterized using two neutron backscattering spectrometers that have overlapping time scales, ranging from picoseconds to a few nanoseconds. Two modes of motion are detected for the PEI molecule in QENS. At low energy transfers, a “slow process” on the time scale of ~200 ps is found and attributed to jump-mediated, center-of-mass diffusion. Second, a “fast process” at ~20 ps scale is also found and is attributed to a locally confined, jump-diffusion. Characteristic data (time scale and spectral weight) of these processes are compared to those characterized by MD, and reasonable agreement is found. For the nanopore-confined PEI, we observe a significant reduction in the time scale of polymer motion as compared to the bulk. The impacts of silica surface functionalization and of polymer fill fraction in the silica pores (controlling the portion of polymer molecules in contact with the pore walls), are both studied in detail. Hydrophobic functionalization of the silica leads to an increase of the PEI mobility above that in native silanol-terminated silica, but the dynamics are still slower than those in bulk PEI. Sorbents with faster PEI dynamics are also found to be more efficient for CO2 capture, possibly because sorption sites are more accessible than those in systems with slower PEI dynamics. Therefore, this work supports the existence of a link between the affinity of the support for PEI and the accessibility of active sorbent functional groups.},
doi = {10.1021/acs.jpcb.7b04106},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 27,
volume = 121,
place = {United States},
year = {Tue May 30 00:00:00 EDT 2017},
month = {Tue May 30 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Amine-oxide hybrid materials for acid gas separations
journal, January 2011
- Bollini, Praveen; Didas, Stephanie A.; Jones, Christopher W.
- Journal of Materials Chemistry, Vol. 21, Issue 39
Amine-Based CO 2 Capture Technology Development from the Beginning of 2013—A Review
journal, January 2015
- Dutcher, Bryce; Fan, Maohong; Russell, Armistead G.
- ACS Applied Materials & Interfaces, Vol. 7, Issue 4
CO2 capture by amine-functionalized nanoporous materials: A review
journal, October 2014
- Chen, Chao; Kim, Jun; Ahn, Wha-Seung
- Korean Journal of Chemical Engineering, Vol. 31, Issue 11
Sorbents for CO2 capture from flue gas—aspects from materials and theoretical chemistry
journal, January 2010
- Hedin, Niklas; Chen, LiJun; Laaksonen, Aatto
- Nanoscale, Vol. 2, Issue 10
Three-dimensional molecular basket sorbents for CO2 capture: Effects of pore structure of supports and loading level of polyethylenimine
journal, September 2014
- Wang, Dongxiang; Wang, Xiaoxing; Ma, Xiaoliang
- Catalysis Today, Vol. 233
Dramatic Enhancement of CO 2 Uptake by Poly(ethyleneimine) Using Zirconosilicate Supports
journal, June 2012
- Kuwahara, Yasutaka; Kang, Dun-Yen; Copeland, John R.
- Journal of the American Chemical Society, Vol. 134, Issue 26
CO2 adsorption on amine modified mesoporous silicas: Effect of the progressive disorder of the honeycomb arrangement
journal, June 2015
- Vilarrasa-Garcia, E.; Moya, E. M. Ortigosa; Cecilia, J. A.
- Microporous and Mesoporous Materials, Vol. 209
Amine-Modified SBA-15: Effect of Pore Structure on the Performance for CO 2 Capture
journal, March 2011
- Yan, Xinlong; Zhang, Lei; Zhang, Ying
- Industrial & Engineering Chemistry Research, Vol. 50, Issue 6
Amine-modified ordered mesoporous silica: The effect of pore size on CO2 capture performance
journal, January 2015
- Wang, Lin; Yao, Manli; Hu, Xin
- Applied Surface Science, Vol. 324
Effect of the Pore Length on CO 2 Adsorption over Amine-Modified Mesoporous Silicas
journal, September 2011
- Heydari-Gorji, Aliakbar; Yang, Yong; Sayari, Abdelhamid
- Energy & Fuels, Vol. 25, Issue 9
CO2 adsorption on Santa Barbara Amorphous-15 (SBA-15) and amine-modified Santa Barbara Amorphous-15 (SBA-15) with and without controlled microporosity
journal, January 2013
- Yan, Xinlong; Komarneni, Sridhar; Yan, Zifeng
- Journal of Colloid and Interface Science, Vol. 390, Issue 1
Polyethylenimine-Impregnated Mesoporous Silica: Effect of Amine Loading and Surface Alkyl Chains on CO 2 Adsorption
journal, October 2011
- Heydari-Gorji, Aliakbar; Belmabkhout, Youssef; Sayari, Abdelhamid
- Langmuir, Vol. 27, Issue 20
CO2 Capture by As-Prepared SBA-15 with an Occluded Organic Template
journal, September 2006
- Yue, M. B.; Chun, Y.; Cao, Y.
- Advanced Functional Materials, Vol. 16, Issue 13
Effect of Pore Structure on CO 2 Adsorption Characteristics of Aminopolymer Impregnated MCM-36
journal, April 2015
- Cogswell, Christopher F.; Jiang, Hui; Ramberger, Justin
- Langmuir, Vol. 31, Issue 15
Role of Amine Structure on Carbon Dioxide Adsorption from Ultradilute Gas Streams such as Ambient Air
journal, July 2012
- Didas, Stephanie A.; Kulkarni, Ambarish R.; Sholl, David S.
- ChemSusChem, Vol. 5, Issue 10, p. 2058-2064
FTIR Study of CO2 Adsorption on Amine-Grafted SBA-15: Elucidation of Adsorbed Species
journal, May 2011
- Danon, Alon; Stair, Peter C.; Weitz, Eric
- The Journal of Physical Chemistry C, Vol. 115, Issue 23, p. 11540-11549
Periodic mesoporous organosilicas functionalized with a wide variety of amines for CO2 adsorption
journal, January 2013
- De Canck, Els; Ascoop, Isabelle; Sayari, Abdelhamid
- Physical Chemistry Chemical Physics, Vol. 15, Issue 24
Important Roles of Enthalpic and Entropic Contributions to CO 2 Capture from Simulated Flue Gas and Ambient Air Using Mesoporous Silica Grafted Amines
journal, September 2014
- Alkhabbaz, Mustafa A.; Bollini, Praveen; Foo, Guo Shiou
- Journal of the American Chemical Society, Vol. 136, Issue 38
Linking CO 2 Sorption Performance to Polymer Morphology in Aminopolymer/Silica Composites through Neutron Scattering
journal, September 2015
- Holewinski, Adam; Sakwa-Novak, Miles A.; Jones, Christopher W.
- Journal of the American Chemical Society, Vol. 137, Issue 36
Steam Induced Structural Changes of a Poly(ethylenimine) Impregnated γ-Alumina Sorbent for CO 2 Extraction from Ambient Air
journal, June 2014
- Sakwa-Novak, Miles A.; Jones, Christopher W.
- ACS Applied Materials & Interfaces, Vol. 6, Issue 12
Enhanced Adsorption Efficiency through Materials Design for Direct Air Capture over Supported Polyethylenimine
journal, September 2016
- Sayari, Abdelhamid; Liu, Qing; Mishra, Prashant
- ChemSusChem, Vol. 9, Issue 19
Poly(allylamine)–Mesoporous Silica Composite Materials for CO 2 Capture from Simulated Flue Gas or Ambient Air
journal, December 2011
- Chaikittisilp, Watcharop; Khunsupat, Ratayakorn; Chen, Thomas T.
- Industrial & Engineering Chemistry Research, Vol. 50, Issue 24
Surfactant promoted solid amine sorbents for CO 2 capture
journal, January 2012
- Wang, Jitong; Long, Donghui; Zhou, Huanhuan
- Energy Environ. Sci., Vol. 5, Issue 2
Role of Additives in Composite PEI/Oxide CO 2 Adsorbents: Enhancement in the Amine Efficiency of Supported PEI by PEG in CO 2 Capture from Simulated Ambient Air
journal, November 2015
- Sakwa-Novak, Miles A.; Tan, Shuai; Jones, Christopher W.
- ACS Applied Materials & Interfaces, Vol. 7, Issue 44
Control of CO 2 Adsorption and Desorption Using Polyethylene Glycol in a Tetraethylenepentamine Thin Film: An In Situ ATR and Theoretical Study
journal, October 2016
- Miller, Duane D.; Chuang, Steven S. C.
- The Journal of Physical Chemistry C, Vol. 120, Issue 44
Statistical Mechanical Theory of Penetrant Diffusion in Polymer Melts and Glasses
journal, July 2016
- Zhang, Rui; Schweizer, Kenneth S.
- Macromolecules, Vol. 49, Issue 15
Transport Properties of Amine/Carbon Dioxide Reactive Mixtures and Implications to Carbon Capture Technologies
journal, August 2015
- Turgman-Cohen, Salomon; Giannelis, Emmanuel P.; Escobedo, Fernando A.
- ACS Applied Materials & Interfaces, Vol. 7, Issue 32
Transport, Zwitterions, and the Role of Water for CO 2 Adsorption in Mesoporous Silica-Supported Amine Sorbents
journal, December 2013
- Mebane, David S.; Kress, Joel D.; Storlie, Curtis B.
- The Journal of Physical Chemistry C, Vol. 117, Issue 50
Unraveling the Dynamics of Aminopolymer/Silica Composites
journal, March 2016
- Carrillo, Jan-Michael Y.; Sakwa-Novak, Miles A.; Holewinski, Adam
- Langmuir, Vol. 32, Issue 11
Morphology-selective synthesis of mesoporous SBA-15 particles over micrometer, submicrometer and nanometer scales
journal, January 2010
- Lee, Hyung Ik; Kim, Jin Hoe; Stucky, Galen D.
- Journal of Materials Chemistry, Vol. 20, Issue 39
True Microporosity and Surface Area of Mesoporous SBA-15 Silicas as a Function of Synthesis Temperature
journal, December 2001
- Galarneau, Anne; Cambon, Hélène; Di Renzo, Francesco
- Langmuir, Vol. 17, Issue 26
Probing the Role of Zr Addition versus Textural Properties in Enhancement of CO 2 Adsorption Performance in Silica/PEI Composite Sorbents
journal, August 2015
- Sakwa-Novak, Miles A.; Holewinski, Adam; Hoyt, Caroline B.
- Langmuir, Vol. 31, Issue 34
Physical adsorption characterization of nanoporous materials: progress and challenges
journal, February 2014
- Thommes, Matthias; Cychosz, Katie A.
- Adsorption, Vol. 20, Issue 2-3
Density functional theory methods for characterization of porous materials
journal, November 2013
- Landers, John; Gor, Gennady Yu.; Neimark, Alexander V.
- Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 437
BASIS: A New Backscattering Spectrometer at the SNS
journal, July 2008
- Mamontov, E.; Zamponi, M.; Hammons, S.
- Neutron News, Vol. 19, Issue 3
The high-flux backscattering spectrometer at the NIST Center for Neutron Research
journal, May 2003
- Meyer, A.; Dimeo, R. M.; Gehring, P. M.
- Review of Scientific Instruments, Vol. 74, Issue 5
DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009
- Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
- Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
Structure and dynamics of confined flexible and unentangled polymer melts in highly adsorbing cylindrical pores
journal, August 2014
- Carrillo, Jan-Michael Y.; Sumpter, Bobby G.
- The Journal of Chemical Physics, Vol. 141, Issue 7
Onsets of Anharmonicity in Protein Dynamics
journal, July 2005
- Roh, J. H.; Novikov, V. N.; Gregory, R. B.
- Physical Review Letters, Vol. 95, Issue 3
Methyl Group Dynamics in Glassy Polyisoprene: A Neutron Backscattering Investigation
journal, July 1994
- Frick, B.; Fetters, L. J.
- Macromolecules, Vol. 27, Issue 4
Diffusive Motions in Water and Cold Neutron Scattering
journal, August 1960
- Singwi, K. S.; Sjölander, Alf
- Physical Review, Vol. 119, Issue 3
Evidence of a Sticky Boundary Layer in Nanochannels: A Neutron Spin Echo Study of n -Hexatriacontane and Poly(ethylene oxide) Confined in Porous Silicon
journal, October 2010
- Kusmin, André; Gruener, Simon; Henschel, Anke
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 20
Polymer Dynamics in Nanochannels of Porous Silicon: A Neutron Spin Echo Study
journal, October 2010
- Kusmin, André; Gruener, Simon; Henschel, Anke
- Macromolecules, Vol. 43, Issue 19
SynthesisâStructureâProperty Relationships for Hyperbranched Aminosilica CO 2 Adsorbents
journal, December 2009
- Drese, Jeffrey H.; Choi, Sunho; Lively, Ryan P.
- Advanced Functional Materials, Vol. 19, Issue 23
NMR 13C study of the structure of polyethyleneimine
journal, June 1973
- Lukovkin, G. M.; Pshezhetsky, V. S.; Murtazaeva, G. A.
- European Polymer Journal, Vol. 9, Issue 6
A Theory of the Linear Viscoelastic Properties of Dilute Solutions of Coiling Polymers
journal, July 1953
- Rouse, Prince E.
- The Journal of Chemical Physics, Vol. 21, Issue 7
Neutron incoherent scattering law for diffusion in a potential of spherical symmetry: general formalism and application to diffusion inside a sphere
journal, October 1980
- Volino, F.; Dianoux, A. J.
- Molecular Physics, Vol. 41, Issue 2
Proton Dynamics in N , N , N ′, N ′-Tetramethylguanidinium Bis(perfluoroethylsulfonyl)imide Protic Ionic Liquid Probed by Quasielastic Neutron Scattering
journal, January 2009
- Mamontov, Eugene; Luo, Huimin; Dai, Sheng
- The Journal of Physical Chemistry B, Vol. 113, Issue 1
Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media
journal, February 2015
- Huber, Patrick
- Journal of Physics: Condensed Matter, Vol. 27, Issue 10
Effect of Nanoconfinement on Polymer Dynamics: Surface Layers and Interphases
journal, March 2013
- Krutyeva, M.; Wischnewski, A.; Monkenbusch, M.
- Physical Review Letters, Vol. 110, Issue 10
Polymer dynamics in nanoconfinement: Interfaces and interphases
journal, January 2015
- Krutyeva, Margarita; Wischnewski, Andreas; Richter, Dieter
- EPJ Web of Conferences, Vol. 83
Works referencing / citing this record:
Stability of amine-functionalized CO 2 adsorbents: a multifaceted puzzle
journal, January 2019
- Jahandar Lashaki, Masoud; Khiavi, Soheil; Sayari, Abdelhamid
- Chemical Society Reviews, Vol. 48, Issue 12