Underlying Roles of Polyol Additives in Promoting CO2 Capture in PEI/Silica Adsorbents

Moon, Hyun June; Carrillo, Jan-Michael Y.; Song, MinGyu; Rim, Guanhe; Heller, William T.; Leisen, Johannes; Proaño, Laura; Short, Gabriel N.; Banerjee, Sayan; Sumpter, Bobby G.; Jones, Christopher W.

doi:10.1002/cssc.202400967

Underlying Roles of Polyol Additives in Promoting CO2 Capture in PEI/Silica Adsorbents

Journal Article · Mon Jun 03 00:00:00 EDT 2024 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.202400967· OSTI ID:2376352

Moon, Hyun June ^[1]; Carrillo, Jan-Michael Y. ^[2]; Song, MinGyu ^[1]; Rim, Guanhe ^[1]; Heller, William T. ^[2]; Leisen, Johannes ^[1]; Proaño, Laura ^[1]; Short, Gabriel N. ^[1]; Banerjee, Sayan ^[1]; Sumpter, Bobby G. ^[2]; Jones, Christopher W. ^[1]

Georgia Institute of Technology, Atlanta, GA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Solid-supported amines having low molecular weight branched poly(ethylenimine) (PEI) physically impregnated into porous solid supports are promising adsorbents for CO2 capture. Co-impregnating short-chain poly(ethylene glycol) (PEG) together with PEI alters the performance of the adsorbent, delivering improved amine efficiency (AE, mol CO2 sorbed / mol N) and faster CO2 uptake rates. To uncover the physical basis for this improved gas capture performance, we probed the distribution and mobility of the polymers in the pores via small angle neutron scattering (SANS), solid-state NMR, and molecular dynamic (MD) simulation studies. SANS and MD simulations reveal that PEG displaces wall-bound PEI, making amines more accessible for CO2 sorption. Solid-state NMR and MD simulation suggest intercalation of PEG into PEI domains, separating PEI domains and reducing amine-amine interactions, providing potential PEG-rich and amine-poor interfacial domains that bind CO2 weakly via physisorption while providing facile pathways for CO2 diffusion. Contrary to a prior literature hypothesis, no evidence is obtained for PEG facilitating PEI mobility in solid supports. Instead, the data suggest that PEG chains coordinate to PEI, form larger bodies with reduced mobility compared to PEI alone. We also demonstrate promising CO2 uptake and desorption kinetics at varied temperatures, given by favorable amine distribution.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725; SC0012577

OSTI ID:: 2376352

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 22 Vol. 17; ISSN 1864-5631

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Synthesisâ€“Structureâ€“Property Relationships for Hyperbranched Aminosilica CO ₂ Adsorbents Drese, Jeffrey H.; Choi, Sunho; Lively, Ryan P. Advanced Functional Materials, Vol. 19, Issue 23 https://doi.org/10.1002/adfm.200901461	journal	December 2009
Mixed Diethanolamine and Polyethyleneimine with Enhanced CO₂ Capture Capacity from Air Miao, Yihe; Wang, Yaozu; Ge, Bingyao Advanced Science, Vol. 10, Issue 16 https://doi.org/10.1002/advs.202207253	journal	April 2023
In Situ Infrared Study of the Role of PEG in Stabilizing Silica-Supported Amines for CO2 Capture Tanthana, Jak; Chuang, Steven S. C. ChemSusChem, Vol. 3, Issue 8 https://doi.org/10.1002/cssc.201000090	journal	August 2010
Amine-Tethered Solid Adsorbents Coupling High Adsorption Capacity and Regenerability for CO2 Capture From Ambient Air Choi, Sunho; Gray, McMahan L.; Jones, Christopher W. ChemSusChem, Vol. 4, Issue 5 https://doi.org/10.1002/cssc.201000355	journal	May 2011
Spectroscopic Investigation into Oxidative Degradation of Silica-Supported Amine Sorbents for CO2 Capture Srikanth, Chakravartula S.; Chuang, Steven S. C. ChemSusChem, Vol. 5, Issue 8 https://doi.org/10.1002/cssc.201100662	journal	June 2012
Mixed Alkanolamine-Polyethylenimine Functionalized Silica for CO ₂ capture Fan, Yanfang; Rezaei, Fateme; Yang, Xiaomei Energy Technology, Vol. 7, Issue 2 https://doi.org/10.1002/ente.201800481	journal	December 2018
Development and testing of a general amber force field Wang, Junmei; Wolf, Romain M.; Caldwell, James W. Journal of Computational Chemistry, Vol. 25, Issue 9 https://doi.org/10.1002/jcc.20035	journal	January 2004
PACKMOL: A package for building initial configurations for molecular dynamics simulations Martínez, L.; Andrade, R.; Birgin, E. G. Journal of Computational Chemistry, Vol. 30, Issue 13 https://doi.org/10.1002/jcc.21224	journal	October 2009
The reaction between anhydrous ethyleneimine and water Pascoe, P. F.; Sherbrogk‐Gox, W. A. Journal of Applied Chemistry, Vol. 13, Issue 12 https://doi.org/10.1002/jctb.5010131207	journal	December 1963
Probing the solvation shell of organic molecules by intermolecular ¹H NOESY Bagno, Alessandro Journal of Physical Organic Chemistry, Vol. 15, Issue 12 https://doi.org/10.1002/poc.543	journal	November 2002
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Effect of graphene nanoplatelets as nanofiller in plasticized poly(lactic acid) nanocomposites Chieng, Buong Woei; Ibrahim, Nor Azowa; Wan Yunus, Wan Md Zin Journal of Thermal Analysis and Calorimetry, Vol. 118, Issue 3 https://doi.org/10.1007/s10973-014-4084-9	journal	August 2014
Amine-based sorbents for CO2 capture from air and flue gas—a short review and perspective Huhe, Fnu; King, Jaelynne; Chuang, Steven S. C. Research on Chemical Intermediates, Vol. 49, Issue 3 https://doi.org/10.1007/s11164-022-04902-7	journal	January 2023
Research needs targeting direct air capture of carbon dioxide: Material & process performance characteristics under realistic environmental conditions Kong, Fanhe; Rim, Guanhe; Song, MinGyu Korean Journal of Chemical Engineering, Vol. 39, Issue 1 https://doi.org/10.1007/s11814-021-0976-0	journal	January 2022
The reaction of CO2 with ethanolamines Danckwerts, P. V. Chemical Engineering Science, Vol. 34, Issue 4 https://doi.org/10.1016/0009-2509(79)85087-3	journal	January 1979
Comparison of ammonia and monoethanolamine solvents to reduce CO2 greenhouse gas emissions Yeh, An Chin; Bai, Hsunling Science of The Total Environment, Vol. 228, Issue 2-3 https://doi.org/10.1016/S0048-9697(99)00025-X	journal	April 1999
Preparation and characterization of novel CO2 “molecular basket” adsorbents based on polymer-modified mesoporous molecular sieve MCM-41 Xu, Xiaochun; Song, Chunshan; Andrésen, John M. Microporous and Mesoporous Materials, Vol. 62, Issue 1-2 https://doi.org/10.1016/S1387-1811(03)00388-3	journal	August 2003
In vitro and in vivo complement activation and related anaphylactic effects associated with polyethylenimine and polyethylenimine-graft-poly(ethylene glycol) block copolymers Merkel, Olivia M.; Urbanics, Rudolf; Bedőcs, Peter Biomaterials, Vol. 32, Issue 21 https://doi.org/10.1016/j.biomaterials.2011.03.035	journal	July 2011
Implementing molecular dynamics on hybrid high performance computers – short range forces Brown, W. Michael; Wang, Peng; Plimpton, Steven J. Computer Physics Communications, Vol. 182, Issue 4 https://doi.org/10.1016/j.cpc.2010.12.021	journal	April 2011
Poly(vinylalcohol)/poly(ethyleneglycol)/poly(ethyleneimine) blend membranes - structure and CO2 facilitated transport Ben Hamouda, Sofiane; Nguyen, Quang Trong; Langevin, Dominique Comptes Rendus Chimie, Vol. 13, Issue 3 https://doi.org/10.1016/j.crci.2009.10.009	journal	March 2010
CO2 capture over molecular basket sorbents: Effects of SiO2 supports and PEG additive Zhang, Lin; Wang, Xiaoxing; Fujii, Mamoru Journal of Energy Chemistry, Vol. 26, Issue 5 https://doi.org/10.1016/j.jechem.2017.09.002	journal	September 2017
Dual-functional interconnected pebble-like structures in highly crystalline poly(ethylene oxide) membranes for CO2 separation Min, Hyo Jun; Kang, Miso; Lee, Chang Soo Separation and Purification Technology, Vol. 263 https://doi.org/10.1016/j.seppur.2021.118363	journal	May 2021
Direct Capture of CO₂ from Ambient Air Sanz-Pérez, Eloy S.; Murdock, Christopher R.; Didas, Stephanie A. Chemical Reviews, Vol. 116, Issue 19, p. 11840-11876 https://doi.org/10.1021/acs.chemrev.6b00173	journal	August 2016
Enhancing Degradation Resistance of Polyethylenimine for CO ₂ Capture with Cross-Linked Poly(vinyl alcohol) Zhai, Yuxin; Chuang, Steven S. C. Industrial & Engineering Chemistry Research, Vol. 56, Issue 46 https://doi.org/10.1021/acs.iecr.7b03636	journal	November 2017
On the Behavior of the Ethylene Glycol Components of Polydisperse Polyethylene Glycol PEG200 Hoffmann, Markus M.; Too, Matthew D.; Paddock, Nathaniel A. The Journal of Physical Chemistry B, Vol. 127, Issue 5 https://doi.org/10.1021/acs.jpcb.2c06773	journal	January 2023
Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO ₂ Capture Applications: A Quasielastic Neutron Scattering Study Holewinski, Adam; Sakwa-Novak, Miles A.; Carrillo, Jan-Michael Y. The Journal of Physical Chemistry B, Vol. 121, Issue 27 https://doi.org/10.1021/acs.jpcb.7b04106	journal	June 2017
Probing the Morphology and Mobility of Amines in Porous Silica CO₂ Sorbents by ¹H T₁–T₂ Relaxation Correlation NMR Moon, Hyun June; Sekiya, Ryoh-Suke; Jones, Christopher W. The Journal of Physical Chemistry C, Vol. 127, Issue 24 https://doi.org/10.1021/acs.jpcc.3c02441	journal	June 2023
Fundamental Insight into Humid CO₂ Uptake in Direct Air Capture Nanocomposites Using Fluorescence and Portable NMR Relaxometry Russell-Parks, Glory A.; Leick, Noemi; Marple, Maxwell A. T. The Journal of Physical Chemistry C, Vol. 127, Issue 31 https://doi.org/10.1021/acs.jpcc.3c03653	journal	July 2023
Methane Adsorption in Model Mesoporous Material, SBA-15, Studied by Small-Angle Neutron Scattering Chiang, Wei-Shan; Fratini, Emiliano; Baglioni, Piero The Journal of Physical Chemistry C, Vol. 120, Issue 8 https://doi.org/10.1021/acs.jpcc.5b10688	journal	February 2016
Control of CO ₂ Adsorption and Desorption Using Polyethylene Glycol in a Tetraethylenepentamine Thin Film: An In Situ ATR and Theoretical Study Miller, Duane D.; Chuang, Steven S. C. The Journal of Physical Chemistry C, Vol. 120, Issue 44 https://doi.org/10.1021/acs.jpcc.6b09506	journal	October 2016
Unraveling the Dynamics of Aminopolymer/Silica Composites Carrillo, Jan-Michael Y.; Sakwa-Novak, Miles A.; Holewinski, Adam Langmuir, Vol. 32, Issue 11 https://doi.org/10.1021/acs.langmuir.5b04299	journal	March 2016
Linking Silica Support Morphology to the Dynamics of Aminopolymers in Composites Carrillo, Jan-Michael Y.; Potter, Matthew E.; Sakwa-Novak, Miles A. Langmuir, Vol. 33, Issue 22 https://doi.org/10.1021/acs.langmuir.7b00283	journal	May 2017
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 Sakwa-Novak, Miles A.; Tan, Shuai; Jones, Christopher W. ACS Applied Materials & Interfaces, Vol. 7, Issue 44 https://doi.org/10.1021/acsami.5b07545	journal	November 2015
Structures of Partially Fluorinated Bottlebrush Polymers in Thin Films Chang, Dongsook; Lorenz, Matthias; Burch, Matthew J. ACS Applied Polymer Materials, Vol. 2, Issue 2 https://doi.org/10.1021/acsapm.9b00763	journal	December 2019
Polyethylene Glycol (PEG) Addition to Polyethylenimine (PEI)-Impregnated Silica Increases Amine Accessibility during CO ₂ Sorption Wang, Linxi; Al-Aufi, Mohammed; Pacheco, Carlos N. ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 17 https://doi.org/10.1021/acssuschemeng.9b02798	journal	August 2019
In Situ ATR and DRIFTS Studies of the Nature of Adsorbed CO ₂ on Tetraethylenepentamine Films Wilfong, Walter Christopher; Srikanth, Chakravartula S.; Chuang, Steven S. C. ACS Applied Materials & Interfaces, Vol. 6, Issue 16 https://doi.org/10.1021/am5031006	journal	August 2014
Star-Shaped Poly(ethylene glycol)-block-polyethylenimine Copolymers Enhance DNA Condensation of Low Molecular Weight Polyethylenimines Petersen, Holger; Kunath, Klaus; Martin, Alison L. Biomacromolecules, Vol. 3, Issue 5 https://doi.org/10.1021/bm025539z	journal	August 2002
Force Field and a Surface Model Database for Silica to Simulate Interfacial Properties in Atomic Resolution Emami, Fateme S.; Puddu, Valeria; Berry, Rajiv J. Chemistry of Materials, Vol. 26, Issue 8 https://doi.org/10.1021/cm500365c	journal	April 2014
Effect of the Pore Length on CO ₂ Adsorption over Amine-Modified Mesoporous Silicas Heydari-Gorji, Aliakbar; Yang, Yong; Sayari, Abdelhamid Energy & Fuels, Vol. 25, Issue 9 https://doi.org/10.1021/ef200765f	journal	September 2011
Mesoporous Alumina-Supported Amines as Potential Steam-Stable Adsorbents for Capturing CO ₂ from Simulated Flue Gas and Ambient Air Chaikittisilp, Watcharop; Kim, Hyung-Ju; Jones, Christopher W. Energy & Fuels, Vol. 25, Issue 11 https://doi.org/10.1021/ef201224v	journal	November 2011
Mechanisms and kinetics of diethanolamine degradation Kennard, Malcolm L.; Meisen, Axel Industrial & Engineering Chemistry Fundamentals, Vol. 24, Issue 2 https://doi.org/10.1021/i100018a002	journal	May 1985
Carbon Dioxide Reaction Kinetics and Transport in Aqueous Amine Membranes Donaldson, Terrence L.; Nguyen, Yen N. Industrial & Engineering Chemistry Fundamentals, Vol. 19, Issue 3 https://doi.org/10.1021/i160075a005	journal	August 1980
Applications of Pore-Expanded Mesoporous Silicas. 3. Triamine Silane Grafting for Enhanced CO ₂ Adsorption Harlick, Peter J. E.; Sayari, Abdelhamid Industrial & Engineering Chemistry Research, Vol. 45, Issue 9 https://doi.org/10.1021/ie051286p	journal	April 2006
New Insights into the Interactions of CO ₂ with Amine-Functionalized Silica Serna-Guerrero, Rodrigo; Da’na, Enshirah; Sayari, Abdelhamid Industrial & Engineering Chemistry Research, Vol. 47, Issue 23 https://doi.org/10.1021/ie801186g	journal	December 2008
Kinetics of carbamate formation and breakdown Caplow, Michael. Journal of the American Chemical Society, Vol. 90, Issue 24 https://doi.org/10.1021/ja01026a041	journal	November 1968
Designing Adsorbents for CO ₂ Capture from Flue Gas-Hyperbranched Aminosilicas Capable of Capturing CO ₂ Reversibly Hicks, Jason C.; Drese, Jeffrey H.; Fauth, Daniel J. Journal of the American Chemical Society, Vol. 130, Issue 10 https://doi.org/10.1021/ja077795v	journal	March 2008
Understanding the Impacts of Support–Polymer Interactions on the Dynamics of Poly(ethyleneimine) Confined in Mesoporous SBA-15 Moon, Hyun June; Carrillo, Jan-Michael; Leisen, Johannes Journal of the American Chemical Society, Vol. 144, Issue 26 https://doi.org/10.1021/jacs.2c03028	journal	June 2022
Support Pore Structure and Composition Strongly Influence the Direct Air Capture of CO₂ on Supported Amines Rim, Guanhe; Priyadarshini, Pranjali; Song, MinGyu Journal of the American Chemical Society, Vol. 145, Issue 13 https://doi.org/10.1021/jacs.2c12707	journal	March 2023
Linking CO ₂ Sorption Performance to Polymer Morphology in Aminopolymer/Silica Composites through Neutron Scattering Holewinski, Adam; Sakwa-Novak, Miles A.; Jones, Christopher W. Journal of the American Chemical Society, Vol. 137, Issue 36 https://doi.org/10.1021/jacs.5b06823	journal	September 2015
Sub-Ambient Temperature Direct Air Capture of CO₂ using Amine-Impregnated MIL-101(Cr) Enables Ambient Temperature CO₂ Recovery Rim, Guanhe; Kong, Fanhe; Song, Mingyu JACS Au, Vol. 2, Issue 2 https://doi.org/10.1021/jacsau.1c00414	journal	February 2022
The Polymerization of Ethylenimine Jones, Giffin D.; Langsjoen, Arne; Neumann, Sister MARY MARGUERITE CHRISTINE The Journal of Organic Chemistry, Vol. 09, Issue 2 https://doi.org/10.1021/jo01184a002	journal	March 1944
Characterization of Micro- and Mesoporosity in SBA-15 Materials from Adsorption Data by the NLDFT Method Ravikovitch, Peter I.; Neimark, Alexander V. The Journal of Physical Chemistry B, Vol. 105, Issue 29 https://doi.org/10.1021/jp010621u	journal	July 2001
Effect of Amine Surface Coverage on the Co-Adsorption of CO ₂ and Water: Spectral Deconvolution of Adsorbed Species Didas, Stephanie A.; Sakwa-Novak, Miles A.; Foo, Guo Shiou The Journal of Physical Chemistry Letters, Vol. 5, Issue 23 https://doi.org/10.1021/jz502032c	journal	November 2014
Origin of the scattering peak in microemulsions Teubner, M.; Strey, R. The Journal of Chemical Physics, Vol. 87, Issue 5 https://doi.org/10.1063/1.453006	journal	September 1987
Advances in the Chemistry of Polyethyleneimine (Polyaziridine) Zhuk, D. S.; Gembitskii, Petr A.; Kargin, Valentin A. Russian Chemical Reviews, Vol. 34, Issue 7 https://doi.org/10.1070/RC1965v034n07ABEH001499	journal	July 1965
Incorporation and structural arrangement of microemulsion droplets in cylindrical pores of mesoporous silica Prause, Albert; Hörmann, Anja; Cristiglio, Viviana Molecular Physics, Vol. 119, Issue 15-16 https://doi.org/10.1080/00268976.2021.1913255	journal	April 2021
Relaxation Effects in Nuclear Magnetic Resonance Absorption Bloembergen, N.; Purcell, E. M.; Pound, R. V. Physical Review, Vol. 73, Issue 7 https://doi.org/10.1103/PhysRev.73.679	journal	April 1948
Surface relaxation and chemical exchange in hydrating cement pastes: A two-dimensional NMR relaxation study McDonald, P. J.; Korb, J. -P.; Mitchell, J. Physical Review E, Vol. 72, Issue 1 https://doi.org/10.1103/PhysRevE.72.011409	journal	July 2005
The suite of small-angle neutron scattering instruments at Oak Ridge National Laboratory Heller, William T.; Cuneo, Matthew; Debeer-Schmitt, Lisa Journal of Applied Crystallography, Vol. 51, Issue 2 https://doi.org/10.1107/S1600576718001231	journal	February 2018
Effect of Glass‐Transition Temperature of Polyethylene Glycol‐Plasticized Polyvinyl Alcohol on Granule Compaction Nies, C. W.; Messing, G. L. Journal of the American Ceramic Society, Vol. 67, Issue 4 https://doi.org/10.1111/j.1151-2916.1984.tb18852.x	journal	April 1984
Avogadro: an advanced semantic chemical editor, visualization, and analysis platform Hanwell, Marcus D.; Curtis, Donald E.; Lonie, David C. Journal of Cheminformatics, Vol. 4, Issue 1 https://doi.org/10.1186/1758-2946-4-17	journal	August 2012
Computer Simulation Using Particles Hockney, R. W.; Eastwood, J. W. https://doi.org/10.1201/9780367806934	book	January 1988

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