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Title: Linking CO 2 Sorption Performance to Polymer Morphology in Aminopolymer/Silica Composites through Neutron Scattering

Abstract

Composites of poly(ethylenimine) (PEI) and mesoporous silica are effective, reversible adsorbents for CO2, both from flue gas and in direct air-capture applications. The morphology of the PEI within the silica can strongly impact the overall carbon capture efficiency and rate of saturation. Here, we directly probe the spatial distribution of the supported polymer through small-angle neutron scattering (SANS). Combined with textural characterization from physisorption analysis, the data indicate that PEI first forms a thin conformal coating on the pore walls, but all additional polymer aggregates into plug(s) that grow along the pore axis. This model is consistent with observed trends in amine-efficiency (CO2/N binding ratio) and pore size distributions, and points to a trade-off between achieving high chemical accessibility of the amine binding sites, which are inaccessible when they strongly interact with the silica, and high accessibility for mass transport, which can be hampered by diffusion through PEI plugs. In conclusion, we illustrate this design principle by demonstrating higher CO2 capacity and uptake rate for PEI supported in a hydrophobically modified silica, which exhibits repulsive interactions with the PEI, freeing up binding sites.

Authors:
 [1];  [1];  [1]
  1. School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive, Atlanta, Georgia 30332, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, D.C. (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)
OSTI Identifier:
1213924
Alternate Identifier(s):
OSTI ID: 1386055
Grant/Contract Number:  
SC0012577
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 137 Journal Issue: 36; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); defects; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Holewinski, Adam, Sakwa-Novak, Miles A., and Jones, Christopher W.. Linking CO 2 Sorption Performance to Polymer Morphology in Aminopolymer/Silica Composites through Neutron Scattering. United States: N. p., 2015. Web. doi:10.1021/jacs.5b06823.
Holewinski, Adam, Sakwa-Novak, Miles A., & Jones, Christopher W.. Linking CO 2 Sorption Performance to Polymer Morphology in Aminopolymer/Silica Composites through Neutron Scattering. United States. https://doi.org/10.1021/jacs.5b06823
Holewinski, Adam, Sakwa-Novak, Miles A., and Jones, Christopher W.. 2015. "Linking CO 2 Sorption Performance to Polymer Morphology in Aminopolymer/Silica Composites through Neutron Scattering". United States. https://doi.org/10.1021/jacs.5b06823.
@article{osti_1213924,
title = {Linking CO 2 Sorption Performance to Polymer Morphology in Aminopolymer/Silica Composites through Neutron Scattering},
author = {Holewinski, Adam and Sakwa-Novak, Miles A. and Jones, Christopher W.},
abstractNote = {Composites of poly(ethylenimine) (PEI) and mesoporous silica are effective, reversible adsorbents for CO2, both from flue gas and in direct air-capture applications. The morphology of the PEI within the silica can strongly impact the overall carbon capture efficiency and rate of saturation. Here, we directly probe the spatial distribution of the supported polymer through small-angle neutron scattering (SANS). Combined with textural characterization from physisorption analysis, the data indicate that PEI first forms a thin conformal coating on the pore walls, but all additional polymer aggregates into plug(s) that grow along the pore axis. This model is consistent with observed trends in amine-efficiency (CO2/N binding ratio) and pore size distributions, and points to a trade-off between achieving high chemical accessibility of the amine binding sites, which are inaccessible when they strongly interact with the silica, and high accessibility for mass transport, which can be hampered by diffusion through PEI plugs. In conclusion, we illustrate this design principle by demonstrating higher CO2 capacity and uptake rate for PEI supported in a hydrophobically modified silica, which exhibits repulsive interactions with the PEI, freeing up binding sites.},
doi = {10.1021/jacs.5b06823},
url = {https://www.osti.gov/biblio/1213924}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 36,
volume = 137,
place = {United States},
year = {2015},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1021/jacs.5b06823

Citation Metrics:
Cited by: 18 works
Citation information provided by
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Works referenced in this record:

Size and Spatial Distribution of Micropores in SBA-15 using CM-SANS
journal, September 2011


Structural Characterization of Surfactant Aggregates Adsorbed in Cylindrical Silica Nanopores
journal, May 2011


Scattering by an Inhomogeneous Solid. II. The Correlation Function and Its Application
journal, June 1957


In-situ small-angle neutron scattering study of pore filling and pore emptying in ordered mesoporous silica
journal, December 2009


Small-angle x-ray diffraction of Kr in mesoporous silica: Effects of microporosity and surface roughness
journal, August 2005


Aminopolymer–Silica Composite-Supported Pd Catalysts for Selective Hydrogenation of Alkynes
journal, July 2013


Amine-Functionalized Porous Silicas as Adsorbents for Aldehyde Abatement
journal, June 2013


Diffuse wall structure and narrow mesopores in highly crystalline MCM-41 materials studied by X-ray diffraction
journal, January 1997


Novel Polyethylenimine-Modified Mesoporous Molecular Sieve of MCM-41 Type as High-Capacity Adsorbent for CO2 Capture
journal, November 2002


Global Warming and Carbon-Negative Technology: Prospects for a Lower-Cost Route to a Lower-Risk Atmosphere
journal, October 2009


CO2 adsorption on amine modified mesoporous silicas: Effect of the progressive disorder of the honeycomb arrangement
journal, June 2015


Structure factor for the periodic walls of mesoporous MCM-41 molecular sieves
journal, January 1999


Characterization of Ordered Mesoporous Silica Films Using Small-Angle Neutron Scattering and X-ray Porosimetry
journal, February 2005


Polyethylenimine-Impregnated Mesoporous Silica: Effect of Amine Loading and Surface Alkyl Chains on CO 2 Adsorption
journal, October 2011


True Microporosity and Surface Area of Mesoporous SBA-15 Silicas as a Function of Synthesis Temperature
journal, December 2001


CO2 capture by amine-functionalized nanoporous materials: A review
journal, October 2014


Characterization of the Porous Structure of SBA-15
journal, July 2000


Surfactant Self-Assembly in Cylindrical Silica Nanopores
journal, April 2010


Neutron scattering lengths and cross sections
journal, January 1992


Probing the Adsorption/Desorption of CO 2 on Amine Sorbents by Transient Infrared Studies of Adsorbed CO 2 and C 6 H 6
journal, March 2014


Interrogating the Carbon and Oxygen K-Edge NEXAFS of a CO 2 -Dosed Hyperbranched Aminosilica
journal, December 2014


The extended Q -range small-angle neutron scattering diffractometer at the SNS
journal, July 2010


SANS Investigation of Nitrogen Sorption in Porous Silica
journal, January 2001


Dramatic Enhancement of CO 2 Uptake by Poly(ethyleneimine) Using Zirconosilicate Supports
journal, June 2012


Existence of a Microporous Corona around the Mesopores of Silica-Based SBA-15 Materials Templated by Triblock Copolymers
journal, December 2000


Dynamics of CO 2 Adsorption on Amine Adsorbents. 2. Insights Into Adsorbent Design
journal, November 2012


Aziridine-Functionalized Mesoporous Silica Membranes on Polymeric Hollow Fibers: Synthesis and Single-Component CO 2 and N 2 Permeation Properties
journal, November 2014


Synthesis–Structure–Property Relationships for Hyperbranched Aminosilica CO 2 Adsorbents
journal, December 2009


Diffraction analysis of mesostructured mesoporous materials
journal, January 2013


Amine-modified ordered mesoporous silica: The effect of pore size on CO2 capture performance
journal, January 2015


Physical adsorption characterization of nanoporous materials: progress and challenges
journal, February 2014


Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica Structures
journal, June 1998


Applications of Pore-Expanded Mesoporous Silica. 7. Adsorption of Volatile Organic Compounds
journal, May 2007


Adsorption and Activation of CO2 by Amine-Modified Nanoporous Materials Studied by Solid-State NMR and 13CO2 Adsorption
journal, March 2011


Carbon Dioxide Reaction Kinetics and Transport in Aqueous Amine Membranes
journal, August 1980


Physical Adsorption Characterization of Nanoporous Materials
journal, June 2010


Effect of the Pore Length on CO 2 Adsorption over Amine-Modified Mesoporous Silicas
journal, September 2011


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


An Analytical Approach to Determine the Pore Shape and Size of MCM-41 Materials from X-ray Diffraction Data
journal, June 2006


Simulation of powder diffraction patterns of modified ordered mesoporous materials
journal, January 0001


Block-Copolymer-Templated Ordered Mesoporous Silica:  Array of Uniform Mesopores or Mesopore−Micropore Network?
journal, December 2000


Sorbents for CO2 capture from flue gas—aspects from materials and theoretical chemistry
journal, January 2010


FTIR Study of CO2 Adsorption on Amine-Grafted SBA-15: Elucidation of Adsorbed Species
journal, May 2011


Amine-Modified SBA-15: Effect of Pore Structure on the Performance for CO 2 Capture
journal, March 2011


Tuning Cooperativity by Controlling the Linker Length of Silica-Supported Amines in Catalysis and CO 2 Capture
journal, August 2012

  • Brunelli, Nicholas A.; Didas, Stephanie A.; Venkatasubbaiah, Krishnan
  • Journal of the American Chemical Society, Vol. 134, Issue 34
  • https://doi.org/10.1021/ja305601g

Adsorbent Materials for Carbon Dioxide Capture from Large Anthropogenic Point Sources
journal, September 2009


Aminosilica Materials as Adsorbents for the Selective Removal of Aldehydes and Ketones from Simulated Bio-Oil
journal, January 2011


Pore Structure and Fluid Sorption in Ordered Mesoporous Silica. I. Experimental Study by in situ Small-Angle X-ray Scattering
journal, July 2009


Pore Structure and Fluid Sorption in Ordered Mesoporous Silica. II. Modeling
journal, July 2009


Morphology-selective synthesis of mesoporous SBA-15 particles over micrometer, submicrometer and nanometer scales
journal, January 2010


Amine-Based CO 2 Capture Technology Development from the Beginning of 2013—A Review
journal, January 2015


Mechanisms and Kinetics for Sorption of CO 2 on Bicontinuous Mesoporous Silica Modified with n -Propylamine
journal, September 2011


Scattering by an Inhomogeneous Solid
journal, June 1949


Applications of Pore-Expanded Mesoporous Silica. 1. Removal of Heavy Metal Cations and Organic Pollutants from Wastewater
journal, January 2005


CO2 Capture by As-Prepared SBA-15 with an Occluded Organic Template
journal, September 2006


Physisorbed films in periodic mesoporous silica studied by in situ synchrotron small-angle diffraction
journal, May 2006


Fluid adsorption in ordered mesoporous solids determined by in situ small-angle X-ray scattering
journal, January 2010


Amine-oxide hybrid materials for acid gas separations
journal, January 2011


In Situ ATR and DRIFTS Studies of the Nature of Adsorbed CO 2 on Tetraethylenepentamine Films
journal, August 2014

  • Wilfong, Walter Christopher; Srikanth, Chakravartula S.; Chuang, Steven S. C.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 16
  • https://doi.org/10.1021/am5031006

Effect of Pore Structure on CO 2 Adsorption Characteristics of Aminopolymer Impregnated MCM-36
journal, April 2015


CO 2 Sorption Performance of Composite Polymer/Aminosilica Hollow Fiber Sorbents: An Experimental and Modeling Study
journal, February 2015


Adsorption of Gases in Multimolecular Layers
journal, February 1938


Adsorption of CO 2 -Containing Gas Mixtures over Amine-Bearing Pore-Expanded MCM-41 Silica: Application for Gas Purification
journal, January 2010


Supported Polytertiary Amines: Highly Efficient and Selective SO 2 Adsorbents
journal, January 2014


Steam Induced Structural Changes of a Poly(ethylenimine) Impregnated γ-Alumina Sorbent for CO 2 Extraction from Ambient Air
journal, June 2014


Comparative studies of p6m siliceous mesostructures by powder X-ray diffraction and nitrogen adsorption
journal, April 2007


X-ray structural modeling of silicate mesoporous mesophase material
journal, April 2001


Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores
journal, January 1998


The interpretation of real-space information from small-angle scattering experiments
journal, April 1979


Density functional theory methods for characterization of porous materials
journal, November 2013