Molecular Blends of Methylated-Poly(ethylenimine) and Amorphous Porous Organic Cages for SO2 Adsorption

Zhu, Guanghui; Carrillo, Jan-Michael Y.; Sujan, Achintya; N. Okonkwo, Claudia; Park, Sangjae; Sumpter, Bobby G.; Jones, Christopher W.; Lively, Ryan

doi:10.1039/c8ta02788a

Molecular Blends of Methylated-Poly(ethylenimine) and Amorphous Porous Organic Cages for SO₂ Adsorption

Journal Article · Wed May 30 00:00:00 EDT 2018 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/c8ta02788a· OSTI ID:1439925

Zhu, Guanghui ^[1]; ^[2]; Sujan, Achintya ^[1]; N. Okonkwo, Claudia ^[1]; Park, Sangjae ^[1]; ^[2]; Jones, Christopher W. ^[1]; Lively, Ryan ^[1]

Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical & Biomolecular Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computational Sciences and Engineering Division

Porous organic cages (POCs) are emerging porous materials that exhibit intriguing properties in the areas of self-assembly, host-guest interaction, and solution processability. Here in this work, we explore the applicability of POCs as molecular porous supports for polymeric amines. We find that primary amines in poly(ethylenimine) (PEI) can undergo metathesis with the imine bonds present in POCs, resulting in non-porous products. This problem can be overcome by transforming the primary amines in PEI to tertiary amines via methylation. The methylated PEI (mPEI) forms homogeneous composites with amorphous scrambled porous organic cages (ASPOCs) without undesired reactions or phase separation. The microscopic structure of the composites is studied using molecular dynamics simulations. Finally, these composite materials are evaluated as adsorbents for low concentration SO2 (200 ppm) adsorption and show good thermal and cyclic stability.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

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

OSTI ID:: 1439925

Alternate ID(s):: OSTI ID: 1441050

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 44 Vol. 6; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

CO2 Capture by As-Prepared SBA-15 with an Occluded Organic Template Yue, M. B.; Chun, Y.; Cao, Y. Advanced Functional Materials, Vol. 16, Issue 13 https://doi.org/10.1002/adfm.200600427	journal	September 2006
Surface Functionalization of Porous Coordination Nanocages Via Click Chemistry and Their Application in Drug Delivery Zhao, Dan; Tan, Songwei; Yuan, Daqiang Advanced Materials, Vol. 23, Issue 1 https://doi.org/10.1002/adma.201003012	journal	October 2010
Porous Organic Cage Thin Films and Molecular-Sieving Membranes Song, Qilei; Jiang, Shan; Hasell, Tom Advanced Materials, Vol. 28, Issue 13 https://doi.org/10.1002/adma.201505688	journal	January 2016
Microporous Organic Materials for Membrane-Based Gas Separation Zou, Xiaoqin; Zhu, Guangshan Advanced Materials, Vol. 30, Issue 3 https://doi.org/10.1002/adma.201700750	journal	October 2017
On-Off Porosity Switching in a Molecular Organic Solid Jones, James T. A.; Holden, Daniel; Mitra, Tamoghna Angewandte Chemie, Vol. 123, Issue 3 https://doi.org/10.1002/ange.201006030	journal	November 2010
Radical Polymerization of Vinyl Monomers in Porous Organic Cages Uemura, Takashi; Nakanishi, Ryo; Mochizuki, Shuto Angewandte Chemie, Vol. 128, Issue 22 https://doi.org/10.1002/ange.201601587	journal	March 2016
Oriented Two‐Dimensional Porous Organic Cage Crystals Jiang, Shan; Song, Qilei; Massey, Alan Angewandte Chemie, Vol. 129, Issue 32 https://doi.org/10.1002/ange.201704579	journal	July 2017
On-Off Porosity Switching in a Molecular Organic Solid Jones, James T. A.; Holden, Daniel; Mitra, Tamoghna Angewandte Chemie International Edition, Vol. 50, Issue 3 https://doi.org/10.1002/anie.201006030	journal	November 2010
Radical Polymerization of Vinyl Monomers in Porous Organic Cages Uemura, Takashi; Nakanishi, Ryo; Mochizuki, Shuto Angewandte Chemie International Edition, Vol. 55, Issue 22 https://doi.org/10.1002/anie.201601587	journal	March 2016
Mixed-Matrix Membranes Dechnik, Janina; Gascon, Jorge; Doonan, Christian J. Angewandte Chemie International Edition, Vol. 56, Issue 32 https://doi.org/10.1002/anie.201701109	journal	July 2017
Oriented Two-Dimensional Porous Organic Cage Crystals Jiang, Shan; Song, Qilei; Massey, Alan Angewandte Chemie International Edition, Vol. 56, Issue 32 https://doi.org/10.1002/anie.201704579	journal	July 2017
Thermally reversible polymeric sorbents for acid gases: CO2, SO2, and NOx Diaf, Abderrahmane; Garcia, Jose L.; Beckman, Eric J. Journal of Applied Polymer Science, Vol. 53, Issue 7 https://doi.org/10.1002/app.1994.070530703	journal	August 1994
Engineering Porous Organic Cage Crystals with Increased Acid Gas Resistance Zhu, Guanghui; Hoffman, Christopher D.; Liu, Yang Chemistry - A European Journal, Vol. 22, Issue 31 https://doi.org/10.1002/chem.201601659	journal	June 2016
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
Role of Alumina Basicity in CO ₂ Uptake in 3-Aminopropylsilyl-Grafted Alumina Adsorbents Potter, Matthew E.; Cho, Kyeong Min; Lee, Jason J. ChemSusChem, Vol. 10, Issue 10 https://doi.org/10.1002/cssc.201700115	journal	April 2017
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
Simultaneous removal of SO2, NO and particulate by pilot-scale scrubber system Jung, Seung-Ho; Jeong, Gwi-Taek; Lee, Gwang-Yeon Korean Journal of Chemical Engineering, Vol. 24, Issue 6 https://doi.org/10.1007/s11814-007-0122-7	journal	November 2007
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
Rate-based modelling of SO2 absorption into aqueous NaHCO3/Na2CO3 solutions accompanied by the desorption of CO2 Ebrahimi, S.; Picioreanu, C.; Kleerebezem, R. Chemical Engineering Science, Vol. 58, Issue 16 https://doi.org/10.1016/S0009-2509(03)00231-8	journal	August 2003
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
The Reaction of CO₂ with Ethanolamines Danckwerts, P. V. Insights Into Chemical Engineering, p. 208-212 https://doi.org/10.1016/b978-0-08-026250-5.50039-3	book	January 1981
A chiral porous organic cage for molecular recognition using gas chromatography Xie, Sheng-Ming; Zhang, Jun-Hui; Fu, Nan Analytica Chimica Acta, Vol. 903 https://doi.org/10.1016/j.aca.2015.11.030	journal	January 2016
Selective removal of SO2 over tertiary amine-containing materials Tailor, Ritesh; Ahmadalinezhad, Asieh; Sayari, Abdelhamid Chemical Engineering Journal, Vol. 240 https://doi.org/10.1016/j.cej.2013.11.002	journal	March 2014
Grafted propyldiethanolamine for selective removal of SO 2 in the presence of CO 2 Tailor, Ritesh; Sayari, Abdelhamid Chemical Engineering Journal, Vol. 289 https://doi.org/10.1016/j.cej.2015.12.084	journal	April 2016
Human health effects of air pollution Kampa, Marilena; Castanas, Elias Environmental Pollution, Vol. 151, Issue 2 https://doi.org/10.1016/j.envpol.2007.06.012	journal	January 2008
CO₂ capture by adsorption with nitrogen enriched carbons Plaza, M. G.; Pevida, C.; Arenillas, A. Fuel, Vol. 86, Issue 14, p. 2204-2212 https://doi.org/10.1016/j.fuel.2007.06.001	journal	September 2007
Adsorption separation of carbon dioxide from flue gas of natural gas-fired boiler by a novel nanoporous “molecular basket” adsorbent Xu, Xiaochun; Song, Chunshan; Miller, Bruce G. Fuel Processing Technology, Vol. 86, Issue 14-15 https://doi.org/10.1016/j.fuproc.2005.01.002	journal	October 2005
Semi-batch absorption and regeneration studies for CO2 capture by aqueous ammonia Yeh, James T.; Resnik, Kevin P.; Rygle, Kathy Fuel Processing Technology, Vol. 86, Issue 14-15 https://doi.org/10.1016/j.fuproc.2005.01.015	journal	October 2005
A review on solid adsorbents for carbon dioxide capture Lee, Seul-Yi; Park, Soo-Jin Journal of Industrial and Engineering Chemistry, Vol. 23 https://doi.org/10.1016/j.jiec.2014.09.001	journal	March 2015
Adsorptive removal of carbon dioxide using polyethyleneimine-loaded mesoporous silica materials Son, Won-Jin; Choi, Jung-Sik; Ahn, Wha-Seung Microporous and Mesoporous Materials, Vol. 113, Issue 1-3 https://doi.org/10.1016/j.micromeso.2007.10.049	journal	August 2008
Degradation of amine-supported CO2 adsorbents in the presence of oxygen-containing gases Heydari-Gorji, Aliakbar; Belmabkhout, Youssef; Sayari, Abdelhamid Microporous and Mesoporous Materials, Vol. 145, Issue 1-3 https://doi.org/10.1016/j.micromeso.2011.05.010	journal	November 2011
An overview of current status of carbon dioxide capture and storage technologies Leung, Dennis Y. C.; Caramanna, Giorgio; Maroto-Valer, M. Mercedes Renewable and Sustainable Energy Reviews, Vol. 39 https://doi.org/10.1016/j.rser.2014.07.093	journal	November 2014
Amine–Oxide Hybrid Materials for CO ₂ Capture from Ambient Air Didas, Stephanie A.; Choi, Sunho; Chaikittisilp, Watcharop Accounts of Chemical Research, Vol. 48, Issue 10 https://doi.org/10.1021/acs.accounts.5b00284	journal	September 2015
Formation Mechanisms and Defect Engineering of Imine-Based Porous Organic Cages Zhu, Guanghui; Liu, Yang; Flores, Luis Chemistry of Materials, Vol. 30, Issue 1 https://doi.org/10.1021/acs.chemmater.7b04323	journal	December 2017
Amine Molecular Cages as Supramolecular Fluorescent Explosive Sensors: A Computational Perspective Zwijnenburg, Martijn A.; Berardo, Enrico; Peveler, William J. The Journal of Physical Chemistry B, Vol. 120, Issue 22 https://doi.org/10.1021/acs.jpcb.6b03059	journal	May 2016
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
Oxidative Degradation of Aminosilica Adsorbents Relevant to Postcombustion CO ₂ Capture Bollini, Praveen; Choi, Sunho; Drese, Jeffrey H. Energy & Fuels, Vol. 25, Issue 5 https://doi.org/10.1021/ef200140z	journal	May 2011
Supported Polytertiary Amines: Highly Efficient and Selective SO ₂ Adsorbents Tailor, Ritesh; Abboud, Mohamed; Sayari, Abdelhamid Environmental Science & Technology, Vol. 48, Issue 3 https://doi.org/10.1021/es404135j	journal	January 2014
Influence of Moisture on CO ₂ Separation from Gas Mixture by a Nanoporous Adsorbent Based on Polyethylenimine-Modified Molecular Sieve MCM-41 Xu, Xiaochun; Song, Chunshan; Miller, Bruce G. Industrial & Engineering Chemistry Research, Vol. 44, Issue 21 https://doi.org/10.1021/ie050382n	journal	October 2005
Selective Adsorption of SO ₂ from Flue Gas on Triethanolamine-Modified Large Pore SBA-15 Zhi, Yongting; Zhou, Yaping; Su, Wei Industrial & Engineering Chemistry Research, Vol. 50, Issue 14 https://doi.org/10.1021/ie2004658	journal	July 2011
Effects of O ₂ and SO ₂ on the Capture Capacity of a Primary-Amine Based Polymeric CO ₂ Sorbent Hallenbeck, Alexander P.; Kitchin, John R. Industrial & Engineering Chemistry Research, Vol. 52, Issue 31 https://doi.org/10.1021/ie400582a	journal	July 2013
Supramolecular Engineering of Intrinsic and Extrinsic Porosity in Covalent Organic Cages Bojdys, Michael J.; Briggs, Michael E.; Jones, James T. A. Journal of the American Chemical Society, Vol. 133, Issue 41 https://doi.org/10.1021/ja2056374	journal	October 2011
Toward Homogenization of Heterogeneous Metal Nanoparticle Catalysts with Enhanced Catalytic Performance: Soluble Porous Organic Cage as a Stabilizer and Homogenizer Sun, Jian-Ke; Zhan, Wen-Wen; Akita, Tomoki Journal of the American Chemical Society, Vol. 137, Issue 22 https://doi.org/10.1021/jacs.5b04029	journal	June 2015
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
Porous Organic Cages for Sulfur Hexafluoride Separation Hasell, Tom; Miklitz, Marcin; Stephenson, Andrew Journal of the American Chemical Society, Vol. 138, Issue 5 https://doi.org/10.1021/jacs.5b11797	journal	January 2016
Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C ₇₀ -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium Ortiz, Michael; Cho, Sung; Niklas, Jens Journal of the American Chemical Society, Vol. 139, Issue 12 https://doi.org/10.1021/jacs.7b00220	journal	March 2017
Design of Aminopolymer Structure to Enhance Performance and Stability of CO ₂ Sorbents: Poly(propylenimine) vs Poly(ethylenimine) Pang, Simon H.; Lee, Li-Chen; Sakwa-Novak, Miles A. Journal of the American Chemical Society, Vol. 139, Issue 10 https://doi.org/10.1021/jacs.7b00235	journal	March 2017
Fast Method for Computing Pore Size Distributions of Model Materials Bhattacharya, Supriyo; Gubbins, Keith E. Langmuir, Vol. 22, Issue 18 https://doi.org/10.1021/la052651k	journal	August 2006
Synthesis, Characterization, and Carbon Dioxide Adsorption of Covalently Attached Polyethyleneimine-Functionalized Single-Wall Carbon Nanotubes Dillon, Eoghan P.; Crouse, Christopher A.; Barron, Andrew R. ACS Nano, Vol. 2, Issue 1 https://doi.org/10.1021/nn7002713	journal	January 2008
Liquids with permanent porosity Giri, Nicola; Del Pópolo, Mario G.; Melaugh, Gavin Nature, Vol. 527, Issue 7577 https://doi.org/10.1038/nature16072	journal	November 2015
Porous organic molecular solids by dynamic covalent scrambling Jiang, Shan; Jones, James T. A.; Hasell, Tom Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1207	journal	February 2011
Review of solutions to global warming, air pollution, and energy security Jacobson, Mark Z. Energy Environ. Sci., Vol. 2, Issue 2 https://doi.org/10.1039/B809990C	journal	January 2009
Toxic gas removal – metal–organic frameworks for the capture and degradation of toxic gases and vapours Barea, Elisa; Montoro, Carmen; Navarro, Jorge A. R. Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C3CS60475F	journal	January 2014
Guest control of structure in porous organic cages Little, Marc A.; Chong, Samantha Y.; Schmidtmann, Marc Chem. Commun., Vol. 50, Issue 67 https://doi.org/10.1039/C4CC04158E	journal	January 2014
An efficient low-temperature route to nitrogen-doping and activation of mesoporous carbons for CO ₂ capture Huang, Kuan; Chai, Song-Hai; Mayes, Richard T. Chemical Communications, Vol. 51, Issue 97 https://doi.org/10.1039/C5CC05619E	journal	January 2015
Functional porous composites by blending with solution-processable molecular pores Jiang, S.; Chen, L.; Briggs, M. E. Chemical Communications, Vol. 52, Issue 42 https://doi.org/10.1039/C6CC01034B	journal	January 2016
Modular assembly of porous organic cage crystals: isoreticular quasiracemates and ternary co-crystal Tothadi, Srinu; Little, Marc A.; Hasell, Tom CrystEngComm, Vol. 19, Issue 33 https://doi.org/10.1039/C7CE00783C	journal	January 2017
A solution-processable dissymmetric porous organic cage Slater, A. G.; Little, M. A.; Briggs, M. E. Molecular Systems Design & Engineering, Vol. 3, Issue 1 https://doi.org/10.1039/C7ME00090A	journal	January 2018
Amine-oxide hybrid materials for acid gas separations Bollini, Praveen; Didas, Stephanie A.; Jones, Christopher W. Journal of Materials Chemistry, Vol. 21, Issue 39 https://doi.org/10.1039/c1jm12522b	journal	January 2011
Alkylated organic cages: from porous crystals to neat liquids Giri, Nicola; Davidson, Christine E.; Melaugh, Gavin Chemical Science, Vol. 3, Issue 6 https://doi.org/10.1039/c2sc01007k	journal	January 2012

Cited By (5)

Molecularly Mixed Composite Membranes for Advanced Separation Processes Zhu, Guanghui; Zhang, Fengyi; Rivera, Matthew P. Angewandte Chemie, Vol. 131, Issue 9 https://doi.org/10.1002/ange.201811341	journal	January 2019
Molecularly Mixed Composite Membranes for Advanced Separation Processes Zhu, Guanghui; Zhang, Fengyi; Rivera, Matthew P. Angewandte Chemie International Edition, Vol. 58, Issue 9 https://doi.org/10.1002/anie.201811341	journal	January 2019
Molecularly Mixed Composite Membranes: Challenges and Opportunities Zhu, Guanghui; O'Nolan, Daniel; Lively, Ryan P. Chemistry – A European Journal, Vol. 26, Issue 16 https://doi.org/10.1002/chem.201903519	journal	March 2020
Stability of amine-functionalized CO ₂ adsorbents: a multifaceted puzzle Jahandar Lashaki, Masoud; Khiavi, Soheil; Sayari, Abdelhamid Chemical Society Reviews, Vol. 48, Issue 12 https://doi.org/10.1039/c8cs00877a	journal	January 2019
Methylated Poly(ethylene)imine Modified Capacitive Micromachined Ultrasonic Transducer for Measurements of CO2 and SO2 in Their Mixtures Barauskas, Dovydas; Pelenis, Donatas; Vanagas, Gailius Sensors, Vol. 19, Issue 14 https://doi.org/10.3390/s19143236	journal	July 2019