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Title: Adsorption Microcalorimetry of CO 2 in Confined Aminopolymers

Abstract

Aminopolymers confined within mesoporous supports have shown promise as materials for direct capture of CO2 from ambient air. In spite of this, relatively little is known about the energetics of CO2 binding in these materials, and the limited calorimetric studies published to date have focused on materials made using molecular aminosilanes rather than amine polymers. In this work, poly(ethylenimine) (PEI) is impregnated within mesoporous SBA-15, and the heats of CO2 adsorption at 30 °C are investigated using a Tian-Calvet calorimeter with emphasis on the role of PEI loading and CO2 pressure in the compositional region relevant to direct capture of CO2 from ambient air. In parallel, CO2 uptakes of these materials are measured using multiple complementary approaches, including both volumetric and gravimetric methods, and distinct changes in uptake as a function of CO2 pressure and amine loading are observed. The CO2 sorption behavior is directly linked to textural data describing the porosity and PEI distribution in the materials.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
Publication Date:
Research Org.:
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)
OSTI Identifier:
1388725
Grant/Contract Number:  
SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 33; Journal Issue: 1; Related Information: UNCAGE-ME partners with Georgia Institute of Technology (lead); Lehigh University; Oak Ridge National Laboratory; University of Alabama; University of Florida; University of Wisconsin; Washington University in St. Louis; Journal ID: ISSN 0743-7463
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

Potter, Matthew E., Pang, Simon H., and Jones, Christopher W. Adsorption Microcalorimetry of CO 2 in Confined Aminopolymers. United States: N. p., 2016. Web. doi:10.1021/acs.langmuir.6b03793.
Potter, Matthew E., Pang, Simon H., & Jones, Christopher W. Adsorption Microcalorimetry of CO 2 in Confined Aminopolymers. United States. https://doi.org/10.1021/acs.langmuir.6b03793
Potter, Matthew E., Pang, Simon H., and Jones, Christopher W. Fri . "Adsorption Microcalorimetry of CO 2 in Confined Aminopolymers". United States. https://doi.org/10.1021/acs.langmuir.6b03793. https://www.osti.gov/servlets/purl/1388725.
@article{osti_1388725,
title = {Adsorption Microcalorimetry of CO 2 in Confined Aminopolymers},
author = {Potter, Matthew E. and Pang, Simon H. and Jones, Christopher W.},
abstractNote = {Aminopolymers confined within mesoporous supports have shown promise as materials for direct capture of CO2 from ambient air. In spite of this, relatively little is known about the energetics of CO2 binding in these materials, and the limited calorimetric studies published to date have focused on materials made using molecular aminosilanes rather than amine polymers. In this work, poly(ethylenimine) (PEI) is impregnated within mesoporous SBA-15, and the heats of CO2 adsorption at 30 °C are investigated using a Tian-Calvet calorimeter with emphasis on the role of PEI loading and CO2 pressure in the compositional region relevant to direct capture of CO2 from ambient air. In parallel, CO2 uptakes of these materials are measured using multiple complementary approaches, including both volumetric and gravimetric methods, and distinct changes in uptake as a function of CO2 pressure and amine loading are observed. The CO2 sorption behavior is directly linked to textural data describing the porosity and PEI distribution in the materials.},
doi = {10.1021/acs.langmuir.6b03793},
journal = {Langmuir},
number = 1,
volume = 33,
place = {United States},
year = {2016},
month = {12}
}

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Cited by: 11 works
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Works referenced in this record:

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

  • Choi, Sunho; Drese, Jeffrey H.; Jones, Christopher W.
  • ChemSusChem, Vol. 2, Issue 9, p. 796-854
  • DOI: 10.1002/cssc.200900036

Post-Combustion CO2 Capture Using Solid Sorbents: A Review
journal, September 2011

  • Samanta, Arunkumar; Zhao, An; Shimizu, George K. H.
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 4, p. 1438-1463
  • DOI: 10.1021/ie200686q

CO2 capture by solid adsorbents and their applications: current status and new trends
journal, January 2011

  • Wang, Qiang; Luo, Jizhong; Zhong, Ziyi
  • Energy Environ. Sci., Vol. 4, Issue 1
  • DOI: 10.1039/C0EE00064G

Predicting Large CO 2 Adsorption in Aluminosilicate Zeolites for Postcombustion Carbon Dioxide Capture
journal, November 2012

  • Kim, Jihan; Lin, Li-Chiang; Swisher, Joseph A.
  • Journal of the American Chemical Society, Vol. 134, Issue 46
  • DOI: 10.1021/ja309818u

Amine loaded zeolites for carbon dioxide capture: Amine loading and adsorption studies
journal, May 2009

  • Chatti, Ravikrishna; Bansiwal, Amit K.; Thote, Jayashri A.
  • Microporous and Mesoporous Materials, Vol. 121, Issue 1-3, p. 84-89
  • DOI: 10.1016/j.micromeso.2009.01.007

Why hybrid porous solids capture greenhouse gases?
journal, January 2011

  • Férey, Gérard; Serre, Christian; Devic, Thomas
  • Chem. Soc. Rev., Vol. 40, Issue 2
  • DOI: 10.1039/C0CS00040J

CO 2 capture and conversion using Mg-MOF-74 prepared by a sonochemical method
journal, January 2012

  • Yang, Da-Ae; Cho, Hye-Young; Kim, Jun
  • Energy Environ. Sci., Vol. 5, Issue 4
  • DOI: 10.1039/C1EE02234B

Post-combustion CO2 capture with a commercial activated carbon: Comparison of different regeneration strategies
journal, September 2010


Aminosilane-Grafted Polymer/Silica Hollow Fiber Adsorbents for CO 2 Capture from Flue Gas
journal, March 2013

  • Rezaei, Fateme; Lively, Ryan P.; Labreche, Ying
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 9
  • DOI: 10.1021/am400636c

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
  • DOI: 10.1002/cssc.201200196

In-Situ Infrared Study of CO 2 Adsorption on SBA-15 Grafted with γ-(Aminopropyl)triethoxysilane
journal, March 2003

  • Chang, Alex C. C.; Chuang, Steven S. C.; Gray, McMahan
  • Energy & Fuels, Vol. 17, Issue 2
  • DOI: 10.1021/ef020176h

CO 2 -Induced Degradation of Amine-Containing Adsorbents: Reaction Products and Pathways
journal, August 2012

  • Sayari, Abdelhamid; Heydari-Gorji, Aliakbar; Yang, Yong
  • Journal of the American Chemical Society, Vol. 134, Issue 33
  • DOI: 10.1021/ja304888a

Infrared Study of CO 2 Sorption over “Molecular Basket” Sorbent Consisting of Polyethylenimine-Modified Mesoporous Molecular Sieve
journal, April 2009

  • Wang, Xiaoxing; Schwartz, Viviane; Clark, Jason C.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 17
  • DOI: 10.1021/jp809946y

Temperature-Induced Uptake of CO 2 and Formation of Carbamates in Mesocaged Silica Modified with n -Propylamines
journal, June 2010

  • Bacsik, Zoltán; Atluri, Rambabu; Garcia-Bennett, Alfonso E.
  • Langmuir, Vol. 26, Issue 12
  • DOI: 10.1021/la1001495

Amine–Oxide Hybrid Materials for CO 2 Capture from Ambient Air
journal, September 2015

  • Didas, Stephanie A.; Choi, Sunho; Chaikittisilp, Watcharop
  • Accounts of Chemical Research, Vol. 48, Issue 10
  • DOI: 10.1021/acs.accounts.5b00284

Amine-bearing mesoporous silica for CO2 removal from dry and humid air
journal, June 2010

  • Belmabkhout, Youssef; Serna-Guerrero, Rodrigo; Sayari, Abdelhamid
  • Chemical Engineering Science, Vol. 65, Issue 11
  • DOI: 10.1016/j.ces.2010.02.044

CO 2 Capture from the Atmosphere and Simultaneous Concentration Using Zeolites and Amine-Grafted SBA-15
journal, December 2011

  • Stuckert, Nicholas R.; Yang, Ralph T.
  • Environmental Science & Technology, Vol. 45, Issue 23
  • DOI: 10.1021/es202647a

Air as the renewable carbon source of the future: an overview of CO2 capture from the atmosphere
journal, January 2012

  • Goeppert, Alain; Czaun, Miklos; Surya Prakash, G. K.
  • Energy & Environmental Science, Vol. 5, Issue 7
  • DOI: 10.1039/c2ee21586a

Spectroscopic Investigation of the Mechanisms Responsible for the Superior Stability of Hybrid Class 1/Class 2 CO 2 Sorbents: A New Class 4 Category
journal, May 2016

  • Wilfong, Walter Christopher; Kail, Brian W.; Jones, Christopher W.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 20
  • DOI: 10.1021/acsami.6b02062

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
  • DOI: 10.1021/la202972t

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

  • Xu, Xiaochun; Song, Chunshan; Andresen, John M.
  • Energy & Fuels, Vol. 16, Issue 6, p. 1463-1469
  • DOI: 10.1021/ef020058u

Thermal and Chemical Stability of Regenerable Solid Amine Sorbent for CO 2 Capture
journal, July 2006

  • Khatri, Rajesh A.; Chuang, Steven S. C.; Soong, Yee
  • Energy & Fuels, Vol. 20, Issue 4
  • DOI: 10.1021/ef050402y

Applications of Pore-Expanded Mesoporous Silicas. 3. Triamine Silane Grafting for Enhanced CO 2 Adsorption
journal, April 2006

  • Harlick, Peter J. E.; Sayari, Abdelhamid
  • Industrial & Engineering Chemistry Research, Vol. 45, Issue 9
  • DOI: 10.1021/ie051286p

Synthesis–Structure–Property 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
  • DOI: 10.1002/adfm.200901461

Adsorptive removal of carbon dioxide using polyethyleneimine-loaded mesoporous silica materials
journal, August 2008


Thermal, Oxidative, and CO 2 -Induced Degradation of Supported Polyethylenimine Adsorbents
journal, May 2012

  • Heydari-Gorji, Aliakbar; Sayari, Abdelhamid
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 19
  • DOI: 10.1021/ie3003446

Preparation and characterization of novel CO2 “molecular basket” adsorbents based on polymer-modified mesoporous molecular sieve MCM-41
journal, August 2003


Polyethylenimine-Impregnated Resin for High CO 2 Adsorption: An Efficient Adsorbent for CO 2 Capture from Simulated Flue Gas and Ambient Air
journal, July 2013

  • Chen, Zhenhe; Deng, Shubo; Wei, Haoran
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 15
  • DOI: 10.1021/am400661b

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
  • DOI: 10.1021/ja303136e

Carbon Dioxide Adsorption onto Polyethylenimine-Functionalized Porous Chitosan Beads
journal, September 2014

  • Fujiki, Junpei; Yogo, Katsunori
  • Energy & Fuels, Vol. 28, Issue 10
  • DOI: 10.1021/ef500975g

Unraveling the Dynamics of Aminopolymer/Silica Composites
journal, March 2016


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
  • DOI: 10.1021/jacs.5b06823

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

  • Wilfong, Walter Christopher; Chuang, Steven S. C.
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 11
  • DOI: 10.1021/ie404403q

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

  • Pinto, Moisés L.; Mafra, Luís; Guil, José M.
  • Chemistry of Materials, Vol. 23, Issue 6, p. 1387-1395
  • DOI: 10.1021/cm1029563

Role of Amine Functionality for CO 2 Chemisorption on Silica
journal, November 2015

  • Hahn, Maximilian W.; Jelic, Jelena; Berger, Edith
  • The Journal of Physical Chemistry B, Vol. 120, Issue 8
  • DOI: 10.1021/acs.jpcb.5b10012

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
  • DOI: 10.1021/jp200914v

Capture of carbon dioxide by polyamine-immobilized mesostructured silica: A solid-state NMR study
journal, January 2017


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

  • Bacsik, Zoltán; Ahlsten, Nanna; Ziadi, Asraa
  • Langmuir, Vol. 27, Issue 17
  • DOI: 10.1021/la202033p

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
  • DOI: 10.1021/am5031006

In Situ Infrared Study of the Effect of Amine Density on the Nature of Adsorbed CO 2 on Amine-Functionalized Solid Sorbents
journal, June 2014

  • Tumuluri, Uma; Isenberg, Mathew; Tan, Chung-Sung
  • Langmuir, Vol. 30, Issue 25
  • DOI: 10.1021/la501284y

Infrared Study of Strongly and Weakly Adsorbed CO 2 on Fresh and Oxidatively Degraded Amine Sorbents
journal, April 2013

  • Srikanth, Chakravartula S.; Chuang, Steven S. C.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 18
  • DOI: 10.1021/jp311232f

Spectroscopic Investigation into Oxidative Degradation of Silica-Supported Amine Sorbents for CO2 Capture
journal, June 2012


Carbon Dioxide Capture with Polyethylenimine-Functionalized Industrial-Grade Multiwalled Carbon Nanotubes
journal, August 2014

  • Liu, Qing; Shi, Junjie; Wang, Qiannan
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 44
  • DOI: 10.1021/ie503118j

Adsorption of CO 2 on amine-functionalised MCM-41: experimental and theoretical studies
journal, January 2015

  • dos Santos, Thiago Custódio; Bourrelly, Sandrine; Llewellyn, Philip L.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 16
  • DOI: 10.1039/C5CP00581G

Modeling CO2 adsorption on amine-functionalized mesoporous silica: 1. A semi-empirical equilibrium model
journal, July 2010

  • Serna-Guerrero, Rodrigo; Belmabkhout, Youssef; Sayari, Abdelhamid
  • Chemical Engineering Journal, Vol. 161, Issue 1-2
  • DOI: 10.1016/j.cej.2010.04.024

Increasing Selective CO 2 Adsorption on Amine-Grafted SBA-15 by Increasing Silanol Density
journal, October 2011

  • Wang, Lifeng; Yang, Ralph T.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 43
  • DOI: 10.1021/jp206976d

Study of the Interaction between Silica Surfaces and the Carbon Dioxide Molecule
journal, September 2010

  • Roque-Malherbe, R.; Polanco-Estrella, R.; Marquez-Linares, F.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 41
  • DOI: 10.1021/jp107754g

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
  • DOI: 10.1021/ja507655x

Probing Intramolecular versus Intermolecular CO 2 Adsorption on Amine-Grafted SBA-15
journal, November 2015


Study of Carbon Dioxide Adsorption on Mesoporous Aminopropylsilane-Functionalized Silica and Titania Combining Microcalorimetry and in Situ Infrared Spectroscopy
journal, December 2009

  • Knöfel, Christina; Martin, Céline; Hornebecq, Virginie
  • The Journal of Physical Chemistry C, Vol. 113, Issue 52
  • DOI: 10.1021/jp907054h

Functionalised micro-/mesoporous silica for the adsorption of carbon dioxide
journal, February 2007


Thermal, Oxidative and CO 2 Induced Degradation of Primary Amines Used for CO 2 Capture: Effect of Alkyl Linker on Stability
journal, May 2014

  • Didas, Stephanie A.; Zhu, Rongshun; Brunelli, Nicholas A.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 23
  • DOI: 10.1021/jp5025137

Evaluating Pore Sizes in Mesoporous Materials:  A Simplified Standard Adsorption Method and a Simplified Broekhoff−de Boer Method
journal, August 1999

  • Lukens,, Wayne W.; Schmidt-Winkel, Patrick; Zhao, Dongyuan
  • Langmuir, Vol. 15, Issue 16
  • DOI: 10.1021/la990209u

Aminosilanes Grafted to Basic Alumina as CO 2 Adsorbents-Role of Grafting Conditions on CO 2 Adsorption Properties
journal, September 2014


Effect of Amine Surface Coverage on the Co-Adsorption of CO 2 and Water: Spectral Deconvolution of Adsorbed Species
journal, November 2014

  • Didas, Stephanie A.; Sakwa-Novak, Miles A.; Foo, Guo Shiou
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 23
  • DOI: 10.1021/jz502032c

Quantification of chemisorption and physisorption of carbon dioxide on porous silica modified by propylamines: Effect of amine density
journal, September 2012


On thermodynamic separation efficiency: Adsorption processes
journal, April 2016

  • Lively, Ryan P.; Realff, Matthew J.
  • AIChE Journal, Vol. 62, Issue 10
  • DOI: 10.1002/aic.15269

Works referencing / citing this record:

Adsorption microcalorimetry as a tool in the characterization of amine-grafted mesoporous silicas for CO2 capture
journal, March 2019


Oxidatively‐Stable Linear Poly(propylenimine)‐Containing Adsorbents for CO 2 Capture from Ultradilute Streams
journal, July 2018

  • Pang, Simon H.; Lively, Ryan P.; Jones, Christopher W.
  • ChemSusChem, Vol. 11, Issue 15
  • DOI: 10.1002/cssc.201800438

CO2 Capture with Mesoporous Silicas Modified with Amines by Double Functionalization: Assessment of Adsorption/Desorption Cycles
journal, May 2018

  • Sánchez-Zambrano, Kléver; Lima Duarte, Lairana; Soares Maia, Débora
  • Materials, Vol. 11, Issue 6
  • DOI: 10.3390/ma11060887

Silica supported poly(propylene guanidine) as a CO2 sorbent in simulated flue gas and direct air capture
journal, November 2019