CO2 Capture Characteristics of Hyperbranched Poly(alkylene imine): A Molecular Dynamics Simulation Approach

Chen, Junhe; Weber Nakamura, Guilherme R.; Jones, Christopher W.; Kwon, Sung Hyun; Jang, Seung Soon

doi:10.1021/acs.jpcb.5c03162

Title: CO₂ Capture Characteristics of Hyperbranched Poly(alkylene imine): A Molecular Dynamics Simulation Approach

Journal Article · Sun Jun 29 00:00:00 UTC 2025 · Journal of Physical Chemistry. B

DOI: https://doi.org/10.1021/acs.jpcb.5c03162 · OSTI ID:2572429

Chen, Junhe ^[1];

^[1]; Jones, Christopher W. ^[1]; Kwon, Sung Hyun ^[2];

^[1]

Georgia Institute of Technology, Atlanta, GA (United States)
Pusan National University (Korea, Republic of)

This study explores the CO₂ capture characteristics of hyperbranched poly(ethylenimine) (HB-PEI) and poly- (propyleneimine) (HB-PPI) through molecular dynamics simulations using density functional theory-calibrated force fields. Key features such as density, free volume, glass transition temperature, CO₂/H₂O distribution, and molecular diffusion are systematically investigated to elucidate structure−function relationships under dry and hydrated conditions. HB-PEI demonstrates a slightly higher density and lower free volume compared to HB-PPI yet shows superior CO₂ capture due to the high amine concentration. Glass transition analysis indicates a higher thermal mobility in HBPEI, enhancing the CO₂ diffusivity. Pair correlation and coordination analyses confirm a stronger affinity of CO₂ with primary and secondary amines, particularly in hydrated environments where water competes with CO₂ for binding sites. Despite its more compact structure, HB-PEI outperformed HB-PPI in CO₂ and H₂O transport, as confirmed by higher diffusion coefficients across all hydration levels. These findings highlight a critical balance among polymer architecture, amine accessibility, and hydration in designing next-generation solid amine sorbents for efficient direct air capture applications.

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Research Organization:: Georgia Institute of Technology, Atlanta, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012577

OSTI ID:: 2572429

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 27 Vol. 129; ISSN 1520-6106; ISSN 1520-5207

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Polyamine-Tethered Porous Polymer Networks for Carbon Dioxide Capture from Flue Gas Lu, Weigang; Sculley, Julian P.; Yuan, Daqiang Angewandte Chemie International Edition, Vol. 51, Issue 30, p. 7480-7484 https://doi.org/10.1002/anie.201202176	journal	June 2012
Adsorbent Materials for Carbon Dioxide Capture from Large Anthropogenic Point Sources Choi, Sunho; Drese, Jeffrey H.; Jones, Christopher W. ChemSusChem, Vol. 2, Issue 9, p. 796-854 https://doi.org/10.1002/cssc.200900036	journal	September 2009
Polyethylenimine Applications in Carbon Dioxide Capture and Separation: From Theoretical Study to Experimental Work Shen, Xinhua; Du, Hongbo; Mullins, Riley H. Energy Technology, Vol. 5, Issue 6 https://doi.org/10.1002/ente.201600694	journal	March 2017
Adsorption characteristics analysis of CO2 and N2 in 13X zeolites by molecular simulation and N2 adsorption experiment Chen, Shujun; Fu, Yue; Huang, Yixiong Journal of Porous Materials, Vol. 23, Issue 3 https://doi.org/10.1007/s10934-016-0126-y	journal	January 2016
The Petlyuk PSA process for the separation of ternary gas mixtures: exemplification by separating a mixture of CO2–CH4–N2 Dong, Fei; Lou, Hongmei; Kodama, Akio Separation and Purification Technology, Vol. 16, Issue 2 https://doi.org/10.1016/S1383-5866(98)00122-1	journal	July 1999
CO2 capture by adsorption: Materials and process development Chaffee, Alan L.; Knowles, Gregory P.; Liang, Zhijian International Journal of Greenhouse Gas Control, Vol. 1, Issue 1 https://doi.org/10.1016/S1750-5836(07)00031-X	journal	April 2007
A review of efficiency penalty in a coal-fired power plant with post-combustion CO2 capture Goto, Kazuya; Yogo, Katsunori; Higashii, Takayuki Applied Energy, Vol. 111 https://doi.org/10.1016/j.apenergy.2013.05.020	journal	November 2013
Toward enhanced CO2 adsorption on bimodal calcium-based materials with porous truncated architectures Kwon, Soonchul; Kwon, Hyuk Jae; Choi, Ji Il Applied Surface Science, Vol. 505 https://doi.org/10.1016/j.apsusc.2019.144512	journal	March 2020
CO2 capture via adsorption in amine-functionalized sorbents Darunte, Lalit A.; Walton, Krista S.; Sholl, David S. Current Opinion in Chemical Engineering, Vol. 12 https://doi.org/10.1016/j.coche.2016.03.002	journal	May 2016
Proton transport through interfaces in nanophase-separation of hydrated aquivion membrane: Molecular dynamics simulation approach Bazaid, Mohammed; Huang, Yu; Goddard, William A. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 676 https://doi.org/10.1016/j.colsurfa.2023.132187	journal	November 2023
A density functional theory (DFT) study of CO2 adsorption on Mg-rich minerals by enhanced charge distribution Kwon, Soonchul; Choi, Ji Il; Lee, Seung Geol Computational Materials Science, Vol. 95 https://doi.org/10.1016/j.commatsci.2014.07.042	journal	December 2014
Process configuration studies of the amine capture process for coal-fired power plants Ahn, Hyungwoong; Luberti, Mauro; Liu, Zhengyi International Journal of Greenhouse Gas Control, Vol. 16 https://doi.org/10.1016/j.ijggc.2013.03.002	journal	August 2013
Ca2CuO3: A high temperature CO2 sorbent with rapid regeneration kinetics Hassani, Ehsan; Cho, Jinwon; Feyzbar-Khalkhali-Nejad, Farshad Journal of Environmental Chemical Engineering, Vol. 10, Issue 2 https://doi.org/10.1016/j.jece.2022.107334	journal	April 2022
Fast magic-angle sample spinning solid-state NMR at 60–100 kHz for natural abundance samples Nishiyama, Yusuke Solid State Nuclear Magnetic Resonance, Vol. 78 https://doi.org/10.1016/j.ssnmr.2016.06.002	journal	September 2016
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
Molecular Simulation Study on Factors Affecting Carbon Dioxide Adsorption on Amorphous Silica Surfaces Kim, Ki Chul; Jang, Seung Soon The Journal of Physical Chemistry C, Vol. 124, Issue 23 https://doi.org/10.1021/acs.jpcc.0c03035	journal	May 2020
Molecular View of CO ₂ Capture by Polyethylenimine: Role of Structural and Dynamical Heterogeneity Sharma, Pragati; Chakrabarty, Suman; Roy, Sudip Langmuir, Vol. 34, Issue 17 https://doi.org/10.1021/acs.langmuir.8b00204	journal	April 2018
Ultrafast ¹H MAS NMR Crystallography for Natural Abundance Pharmaceutical Compounds Struppe, Jochem; Quinn, Caitlin M.; Sarkar, Sucharita Molecular Pharmaceutics, Vol. 17, Issue 2, 674-682 https://doi.org/10.1021/acs.molpharmaceut.9b01157	journal	December 2019
Distribution and Transport of CO₂ in Hyperbranched Poly(ethylenimine)-Loaded MCM-41: A Molecular Dynamics Simulation Approach Chen, Junhe; Moon, Hyun June; Kim, Kyung Il ACS Applied Materials & Interfaces, Vol. 15, Issue 37 https://doi.org/10.1021/acsami.3c07040	journal	September 2023
Enhanced Selectivity for CO₂ Adsorption on Mesoporous Silica with Alkali Metal Halide Due to Electrostatic Field: A Molecular Simulation Approach Kwon, Soonchul; Kwon, Hyuk Jae; Choi, Ji Il ACS Applied Materials & Interfaces, Vol. 9, Issue 37 https://doi.org/10.1021/acsami.7b04508	journal	September 2017
Distribution and Transport of CO₂ in Hydrated Hyperbranched Poly(ethylenimine) Membranes: A Molecular Dynamics Simulation Approach Kim, Kyung Il; Lawler, Robin; Moon, Hyun June ACS Omega, Vol. 6, Issue 4 https://doi.org/10.1021/acsomega.0c05923	journal	January 2021
Dual Alkali Approaches for the Capture and Separation of CO₂ Huang, H. P.; Shi, Y.; Li, W. Energy & Fuels, Vol. 15, Issue 2 https://doi.org/10.1021/ef0002400	journal	February 2001
Adsorption of CO ₂ on Molecular Sieves and Activated Carbon Siriwardane, Ranjani V.; Shen, Ming-Shing; Fisher, Edward P. Energy & Fuels, Vol. 15, Issue 2 https://doi.org/10.1021/ef000241s	journal	March 2001
Novel Polyethylenimine-Modified Mesoporous Molecular Sieve of MCM-41 Type as High-Capacity Adsorbent for CO₂ Capture Xu, Xiaochun; Song, Chunshan; Andresen, John M. Energy & Fuels, Vol. 16, Issue 6, p. 1463-1469 https://doi.org/10.1021/ef020058u	journal	November 2002
CO ₂ Uptake and Adsorption Kinetics of Pore-Expanded SBA-15 Double-Functionalized with Amino Groups Sanz, Raúl; Calleja, Guillermo; Arencibia, Amaya Energy & Fuels, Vol. 27, Issue 12 https://doi.org/10.1021/ef4015229	journal	November 2013
Carbon Dioxide Absorption and Desorption in Aqueous Monoethanolamine Solutions in a Rotating Packed Bed Jassim, Majeed S.; Rochelle, Gary; Eimer, Dag Industrial & Engineering Chemistry Research, Vol. 46, Issue 9 https://doi.org/10.1021/ie051104r	journal	April 2007
Post-Combustion CO₂ Capture Using Solid Sorbents: A Review Samanta, Arunkumar; Zhao, An; Shimizu, George K. H. Industrial & Engineering Chemistry Research, Vol. 51, Issue 4, p. 1438-1463 https://doi.org/10.1021/ie200686q	journal	September 2011
DREIDING: a generic force field for molecular simulations Mayo, Stephen L.; Olafson, Barry D.; Goddard, William A. The Journal of Physical Chemistry, Vol. 94, Issue 26, p. 8897-8909 https://doi.org/10.1021/j100389a010	journal	December 1990
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
Carbon Dioxide Capture from the Air Using a Polyamine Based Regenerable Solid Adsorbent Goeppert, Alain; Czaun, Miklos; May, Robert B. Journal of the American Chemical Society, Vol. 133, Issue 50, p. 20164-20167 https://doi.org/10.1021/ja2100005	journal	December 2011
Structures and Transport Properties of Hydrated Water-Soluble Dendrimer-Grafted Polymer Membranes for Application to Polymer Electrolyte Membrane Fuel Cells: Classical Molecular Dynamics Approach Jang, Seung Soon; Goddard, William A. The Journal of Physical Chemistry C, Vol. 111, Issue 6 https://doi.org/10.1021/jp066014u	journal	January 2007
Carbon Dioxide Capture from Air Using Amine-Grafted Porous Polymer Networks Lu, Weigang; Sculley, Julian P.; Yuan, Daqiang The Journal of Physical Chemistry C, Vol. 117, Issue 8 https://doi.org/10.1021/jp311512q	journal	February 2013
Study of Carbon Dioxide Adsorption on Mesoporous Aminopropylsilane-Functionalized Silica and Titania Combining Microcalorimetry and in Situ Infrared Spectroscopy Knöfel, Christina; Martin, Céline; Hornebecq, Virginie The Journal of Physical Chemistry C, Vol. 113, Issue 52 https://doi.org/10.1021/jp907054h	journal	December 2009
Calibration and Testing of a Water Model for Simulation of the Molecular Dynamics of Proteins and Nucleic Acids in Solution Levitt, Michael; Hirshberg, Miriam; Sharon, Ruth The Journal of Physical Chemistry B, Vol. 101, Issue 25 https://doi.org/10.1021/jp964020s	journal	June 1997
How Impurities Affect CO ₂ Capture in Metal–Organic Frameworks Modified with Different Functional Groups Yu, Jiamei; Balbuena, Perla B. ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 1 https://doi.org/10.1021/sc500607y	journal	November 2014
Unprecedented high-temperature CO₂ selectivity in N₂-phobic nanoporous covalent organic polymers Patel, Hasmukh A.; Hyun Je, Sang; Park, Joonho Nature Communications, Vol. 4, Article No. 1357 https://doi.org/10.1038/ncomms2359	journal	January 2013
CO2 capture by solid adsorbents and their applications: current status and new trends Wang, Qiang; Luo, Jizhong; Zhong, Ziyi Energy Environ. Sci., Vol. 4, Issue 1 https://doi.org/10.1039/C0EE00064G	journal	January 2011
CO₂-selective zeolitic imidazolate framework membrane on graphene oxide nanoribbons: experimental and theoretical studies Choi, Eunji; Hong, Sung Jun; Chen, Junhe Journal of Materials Chemistry A, Vol. 9, Issue 45 https://doi.org/10.1039/D1TA08340F	journal	January 2021
A molecular dynamics simulation study of hydrated sulfonated poly(ether ether ketone) for application to polymer electrolyte membrane fuel cells: Effect of water content Brunello, Giuseppe; Lee, Seung Geol; Jang, Seung Soon Journal of Renewable and Sustainable Energy, Vol. 1, Issue 3 https://doi.org/10.1063/1.3138922	journal	May 2009
Effect of temperature on structure and water transport of hydrated sulfonated poly(ether ether ketone): A molecular dynamics simulation approach Brunello, Giuseppe F.; Mateker, William R.; Lee, Seung Geol Journal of Renewable and Sustainable Energy, Vol. 3, Issue 4 https://doi.org/10.1063/1.3608912	journal	July 2011
⁷ Li NMR Study on Irreversible Capacity of LiNi _0.8-x Co _0.15 Al _0.05 Mg _x O ₂ Electrode in a Lithium-Ion Battery Murakami, Miwa; Shimoda, Keiji; Ukyo, Yoshio Journal of The Electrochemical Society, Vol. 162, Issue 7 https://doi.org/10.1149/2.0781507jes	journal	January 2015
Dendrimeric Systems and Their Applications in Ocular Drug Delivery Yavuz, Burçin; Bozdağ Pehlivan, Sibel; Ünlü, Nurşen The Scientific World Journal, Vol. 2013, Issue 1 https://doi.org/10.1155/2013/732340	journal	January 2013
Study of Hyperbranched Poly(ethyleneimine) Polymers of Different Molecular Weight and Their Interaction with Epoxy Resin Román, Frida; Colomer, Pere; Calventus, Yolanda Materials, Vol. 11, Issue 3 https://doi.org/10.3390/ma11030410	journal	March 2018

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Title: CO2 Capture Characteristics of Hyperbranched Poly(alkylene imine): A Molecular Dynamics Simulation Approach

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Title: CO₂ Capture Characteristics of Hyperbranched Poly(alkylene imine): A Molecular Dynamics Simulation Approach