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Combined CO2-philicity and Ordered Meso-porosity for Highly Selective CO2 Capture at High Temperatures Ji Hoon Lee, Hyeon Jeong Lee, Soo Yeon Lim, Byung Gon Kim, and Jang Wook Choi J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.5b03579 • Publication Date (Web): 22 May 2015 Downloaded from http://pubs.acs.org on May 26, 2015
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Journal of the American Chemical Society is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
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Journal of the American Chemical Society
Combined CO2-philicity and Ordered Meso-porosity for Highly Selective CO2 Capture at High Temperatures Ji Hoon Lee, Hyeon Jeong Lee, Soo Yeon Lim, Byung Gon Kim, and Jang Wook Choi* Graduate School of Energy, Environment, Water, and Sustainability (EEWS), Saudi Aramco-KAIST CO2 Management Center, and Center for Nature-inspired Technology (CNiT) in KAIST Institute NanoCentury, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehakro, Yuseong-gu, Daejeon 305-701, Republic of Korea KEYWORDS: Carbon dioxide (CO2) capture, CO2-Philicity, Melamine resin, Nitrogen content, Ordered mesoporosity, Pore size effect
ABSTRACT: Various dry sorbents have been lately introduced as promising media to capture carbon dioxide (CO2). However, it is still desirable to further improve their performance in diverse aspects, and high temperature selectivity of CO2 over other gases is clearly one of them. Here, we report a co-assembly approach to turn nonporous melamine resin to a highly ordered mesoporous polymeric network (space group: Im-3m) containing high nitrogen content (~18 at%). This mesoporous network shows anomalously increasing CO2/N2 selectivity with temperature rise, with the selectivity at 323 K reaching 117 (Henry method). This selectivity behavior is attributed to a combined effect of the high nitrogen content allowing for high binding affinity with CO2 and well-defined meso-pores (2.5~2.9 nm) accelerating release of N2 with temperature rise. The given orthogonal approach suggests a new direction in designing dry sorbents with excellent selectivities at high temperatures.
1. Introduction The ever-increasing carbon dioxide (CO2) emission from burning fossil fuels has been considered the main origin of various recent environment and energy issues.1, 2 In an effort to overcome this grand challenge, a global integrated measure, namely CO2 capture and sequestration (CCS), has been launched with drawing a great deal of attention and regarded as one of the viable solutions.3-5 In the area of CO2 capture, various kinds of dry sorbents510 have been lately investigated as alternatives to the current commercial technology using aqueous ethanolic amines3, 4 because the commercial technology suffers from intrinsic drawbacks represented by high energy penalty for regeneration and severe corrosion. In spite of the considerable progress so far, it is desirable to further improve performance in key aspects,7 such as total CO2 uptake, CO2 selectivity over other gases especially nitrogen (N2), and uptake retention upon temperature rise. While the performance of dry sorbents is highly dependent on their various material parameters including specific surface area,11, 12 functional group,13-18 and element,19-22 it was recently revealed18-20, 22 that high nitrogen (N)-content can result in high uptake and selectivity simultaneously. In particular, the high selectivity was recently explained by a new concept, so-called N2-phobicity.18 In terms of taking advantage of high N-content, melamine (2,4,6-triamino-1,3,5-triazine) is one of the most ideal moieties for the sorbent building block because of its rich nitrogen content reaching twice as large as carbon. Mel-
amine has additional advantages of low cost and long industrial history.23-25 Despite the high N-content, the widely adopted form of melamine, melamine resin (MR), synthesized via continuous condensation reaction26-31 between melamine and formaldehyde is not appropriate for CO2 capture because its morphology is nonporous and its specific surface area is therefore pretty low (
Article
Combined CO2-philicity and Ordered Meso-porosity for Highly Selective CO2 Capture at High Temperatures Ji Hoon Lee, Hyeon Jeong Lee, Soo Yeon Lim, Byung Gon Kim, and Jang Wook Choi J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.5b03579 • Publication Date (Web): 22 May 2015 Downloaded from http://pubs.acs.org on May 26, 2015
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Journal of the American Chemical Society is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 9
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Journal of the American Chemical Society
Combined CO2-philicity and Ordered Meso-porosity for Highly Selective CO2 Capture at High Temperatures Ji Hoon Lee, Hyeon Jeong Lee, Soo Yeon Lim, Byung Gon Kim, and Jang Wook Choi* Graduate School of Energy, Environment, Water, and Sustainability (EEWS), Saudi Aramco-KAIST CO2 Management Center, and Center for Nature-inspired Technology (CNiT) in KAIST Institute NanoCentury, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehakro, Yuseong-gu, Daejeon 305-701, Republic of Korea KEYWORDS: Carbon dioxide (CO2) capture, CO2-Philicity, Melamine resin, Nitrogen content, Ordered mesoporosity, Pore size effect
ABSTRACT: Various dry sorbents have been lately introduced as promising media to capture carbon dioxide (CO2). However, it is still desirable to further improve their performance in diverse aspects, and high temperature selectivity of CO2 over other gases is clearly one of them. Here, we report a co-assembly approach to turn nonporous melamine resin to a highly ordered mesoporous polymeric network (space group: Im-3m) containing high nitrogen content (~18 at%). This mesoporous network shows anomalously increasing CO2/N2 selectivity with temperature rise, with the selectivity at 323 K reaching 117 (Henry method). This selectivity behavior is attributed to a combined effect of the high nitrogen content allowing for high binding affinity with CO2 and well-defined meso-pores (2.5~2.9 nm) accelerating release of N2 with temperature rise. The given orthogonal approach suggests a new direction in designing dry sorbents with excellent selectivities at high temperatures.
1. Introduction The ever-increasing carbon dioxide (CO2) emission from burning fossil fuels has been considered the main origin of various recent environment and energy issues.1, 2 In an effort to overcome this grand challenge, a global integrated measure, namely CO2 capture and sequestration (CCS), has been launched with drawing a great deal of attention and regarded as one of the viable solutions.3-5 In the area of CO2 capture, various kinds of dry sorbents510 have been lately investigated as alternatives to the current commercial technology using aqueous ethanolic amines3, 4 because the commercial technology suffers from intrinsic drawbacks represented by high energy penalty for regeneration and severe corrosion. In spite of the considerable progress so far, it is desirable to further improve performance in key aspects,7 such as total CO2 uptake, CO2 selectivity over other gases especially nitrogen (N2), and uptake retention upon temperature rise. While the performance of dry sorbents is highly dependent on their various material parameters including specific surface area,11, 12 functional group,13-18 and element,19-22 it was recently revealed18-20, 22 that high nitrogen (N)-content can result in high uptake and selectivity simultaneously. In particular, the high selectivity was recently explained by a new concept, so-called N2-phobicity.18 In terms of taking advantage of high N-content, melamine (2,4,6-triamino-1,3,5-triazine) is one of the most ideal moieties for the sorbent building block because of its rich nitrogen content reaching twice as large as carbon. Mel-
amine has additional advantages of low cost and long industrial history.23-25 Despite the high N-content, the widely adopted form of melamine, melamine resin (MR), synthesized via continuous condensation reaction26-31 between melamine and formaldehyde is not appropriate for CO2 capture because its morphology is nonporous and its specific surface area is therefore pretty low (
