Highly C2/C1-Selective Covalent Organic Frameworks Substituted with Azo Groups

Huang, Shaofeng; Hu, Yiming; Tan, Li-Li; Wan, Shun; Yazdi, Sadegh; Jin, Yinghua; Zhang, Wei

doi:10.1021/acsami.0c15328

Highly C2/C1-Selective Covalent Organic Frameworks Substituted with Azo Groups

Journal Article · Fri Nov 06 00:00:00 EST 2020 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c15328· OSTI ID:1907246

^[1]; Hu, Yiming ^[2]; Tan, Li-Li ^[3]; ^[4]; ^[2]; Jin, Yinghua ^[4]; ^[2]

Univ. of Colorado, Boulder, CO (United States); NCO Technologies LLC
Univ. of Colorado, Boulder, CO (United States)
Northwestern Polytechnical Univ. and Shaanxi Joint Laboratory of Graphene (NPU), Xi’an (China)
NCO Technologies LLC, Longmont, CO (United States)

A series of covalent organic frameworks substituted with azo groups (AzoCOFs) have been synthesized via imine condensation. The obtained frameworks show crystallinity and high stability. More importantly, the AzoCOFs exhibit exceptionally high ideal adsorption solution theory (IAST) selectivity in adsorption of C₂H₂ (35–2891) over CH₄ at 273 K and 1 bar, owing to the favorable interactions between azo groups and acetylene molecules. The dependence of the gas adsorption property on pore size and polarity of the frameworks was also studied. Here, the triethylene glycol substituted Tg-AzoCOF shows the highest C₂H₂/CH₄ selectivity (IAST selectivity of 2891), which represents the highest reported for all porous materials. The AzoCOFs also exhibit high IAST adsorption selectivity of C₂H₄/CH₄ (11–20), C₂H₆/CH₄ (15–22), and CO₂/CH₄ (12–37), which is comparable with most porous materials, thus showing their great potential in gas separation applications.

View Accepted Manuscript (DOE)

Research Organization:: NCO Technologies LLC, Longmont, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Engineering & Technology. Office of Small Business Innovation Research (SBIR) and Small Business Technology Transfer (STTR) Programs

Grant/Contract Number:: SC0017246; SC0019843

OSTI ID:: 1907246

Alternate ID(s):: OSTI ID: 1853399

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 46 Vol. 12; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (25)

Thermodynamics of mixed-gas adsorption Myers, A. L.; Prausnitz, J. M. AIChE Journal, Vol. 11, Issue 1, p. 121-127 https://doi.org/10.1002/aic.690110125	journal	January 1965
A New Approach to Construct a Doubly Interpenetrated Microporous Metal–Organic Framework of Primitive Cubic Net for Highly Selective Sorption of Small Hydrocarbon Molecules Das, Madhab C.; Xu, Hui; Xiang, Shengchang Chemistry – A European Journal, Vol. 17, Issue 28 https://doi.org/10.1002/chem.201100350	journal	May 2011
Covalent Organic Frameworks: Design, Synthesis, and Functions Geng, Keyu; He, Ting; Liu, Ruoyang Chemical Reviews https://doi.org/10.1021/acs.chemrev.9b00550	journal	January 2020
Copper(I)-Catalyzed Synthesis of Nanoporous Azo-Linked Polymers: Impact of Textural Properties on Gas Storage and Selective Carbon Dioxide Capture Arab, Pezhman; Rabbani, Mohammad Gulam; Sekizkardes, Ali Kemal Chemistry of Materials, Vol. 26, Issue 3 https://doi.org/10.1021/cm403161e	journal	January 2014
Basic Raw Materials in the Petrochemical Industry Colten, Oscar A. Industrial & Engineering Chemistry, Vol. 51, Issue 9 https://doi.org/10.1021/ie51396a023	journal	September 1959
Covalent Organic Frameworks as Exceptional Hydrogen Storage Materials Han, Sang Soo; Furukawa, Hiroyasu; Yaghi, Omar M. Journal of the American Chemical Society, Vol. 130, Issue 35, p. 11580-11581 https://doi.org/10.1021/ja803247y	journal	September 2008
Storage of Hydrogen, Methane, and Carbon Dioxide in Highly Porous Covalent Organic Frameworks for Clean Energy Applications Furukawa, Hiroyasu; Yaghi, Omar M. Journal of the American Chemical Society, Vol. 131, Issue 25, p. 8875-8883 https://doi.org/10.1021/ja9015765	journal	July 2009
Constructing Ultraporous Covalent Organic Frameworks in Seconds via an Organic Terracotta Process Karak, Suvendu; Kandambeth, Sharath; Biswal, Bishnu P. Journal of the American Chemical Society, Vol. 139, Issue 5 https://doi.org/10.1021/jacs.6b08815	journal	January 2017
Diacetylene Functionalized Covalent Organic Framework (COF) for Photocatalytic Hydrogen Generation Pachfule, Pradip; Acharjya, Amitava; Roeser, Jérôme Journal of the American Chemical Society, Vol. 140, Issue 4 https://doi.org/10.1021/jacs.7b11255	journal	January 2018
Rationally synthesized two-dimensional polymers Colson, John W.; Dichtel, William R. Nature Chemistry, Vol. 5, Issue 6 https://doi.org/10.1038/nchem.1628	journal	May 2013
Exceptional ammonia uptake by a covalent organic framework Doonan, Christian J.; Tranchemontagne, David J.; Glover, T. Grant Nature Chemistry, Vol. 2, Issue 3, p. 235-238 https://doi.org/10.1038/nchem.548	journal	February 2010
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
Tessellated multiporous two-dimensional covalent organic frameworks Jin, Yinghua; Hu, Yiming; Zhang, Wei Nature Reviews Chemistry, Vol. 1, Issue 7 https://doi.org/10.1038/s41570-017-0056	journal	July 2017
Covalent organic frameworks (COFs): from design to applications Ding, San-Yuan; Wang, Wei Chem. Soc. Rev., Vol. 42, Issue 2 https://doi.org/10.1039/C2CS35072F	journal	January 2013
Facile synthesis of azo-linked porous organic frameworks via reductive homocoupling for selective CO ₂ capture Lu, Jingzhi; Zhang, Jian J. Mater. Chem. A, Vol. 2, Issue 34 https://doi.org/10.1039/C4TA03015J	journal	January 2014
High storage capacity and separation selectivity for C 2 hydrocarbons over methane in the metal–organic framework Cu–TDPAT Liu, Kang; Ma, Dingxuan; Li, Baiyan J. Mater. Chem. A, Vol. 2, Issue 38 https://doi.org/10.1039/C4TA03656E	journal	January 2014
Azo-functionalized microporous organic polymers: synthesis and applications in CO ₂ capture and conversion Yang, Zhenzhen; Zhang, Hongye; Yu, Bo Chemical Communications, Vol. 51, Issue 58 https://doi.org/10.1039/C5CC03151F	journal	January 2015
Separation of C2/C1 hydrocarbons through a gate-opening effect in a microporous metal–organic framework Lin, Rong-Guang; Li, Libo; Lin, Rui-Biao CrystEngComm, Vol. 19, Issue 45 https://doi.org/10.1039/C7CE01766A	journal	January 2017
Efficient separation of C ₂ hydrocarbons in a permanently porous hydrogen-bonded organic framework Yoon, Tae-Ung; Baek, Seung Bin; Kim, Dongwook Chemical Communications, Vol. 54, Issue 67 https://doi.org/10.1039/C8CC04139C	journal	January 2018
An aliphatic hexene-covalent triazine framework for selective acetylene/methane and ethylene/methane separation Krishnaraj, Chidharth; Jena, Himanshu Sekhar; Leus, Karen Journal of Materials Chemistry A, Vol. 7, Issue 21 https://doi.org/10.1039/C8TA11722E	journal	January 2019
A Zn4O-containing doubly interpenetrated porous metal–organic framework for photocatalytic decomposition of methyl orange Das, Madhab C.; Xu, Hui; Wang, Zhiyu Chemical Communications, Vol. 47, Issue 42 https://doi.org/10.1039/c1cc12802g	journal	January 2011
Covalent organic frameworks Feng, Xiao; Ding, Xuesong; Jiang, Donglin Chemical Society Reviews, Vol. 41, Issue 18 https://doi.org/10.1039/c2cs35157a	journal	January 2012
A 3D microporous covalent organic framework with exceedingly high C3H8/CH4 and C2 hydrocarbon/CH4 selectivity Ma, Heping; Ren, Hao; Meng, Shuang Chemical Communications, Vol. 49, Issue 84 https://doi.org/10.1039/c3cc45217d	journal	January 2013
Recent advances in dynamic covalent chemistry Jin, Yinghua; Yu, Chao; Denman, Ryan J. Chemical Society Reviews, Vol. 42, Issue 16 https://doi.org/10.1039/c3cs60044k	journal	January 2013
Porous, Crystalline, Covalent Organic Frameworks Côté, Adrien P.; Benin, Annabelle I.; Ockwig, Nathan W. Science, Vol. 310, Issue 5751, p. 1166-1170 https://doi.org/10.1126/science.1120411	journal	November 2005

Similar Records

Chemical Conversion of Linkages in Covalent Organic Frameworks

Journal Article · Mon Nov 14 19:00:00 EST 2016 · Journal of the American Chemical Society · OSTI ID:1464142

A microporous metal–organic framework for selective C{sub 2}H{sub 2} and CO{sub 2} separation

Journal Article · Tue Aug 15 00:00:00 EDT 2017 · Journal of Solid State Chemistry · OSTI ID:22742022

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C2/C1 separation
adsorption
azo group
covalent organic framework
hydrocarbons
imine condensation
molecules
selective gas adsorption
selectivity

Highly C2/C1-Selective Covalent Organic Frameworks Substituted with Azo Groups

Citation Formats

References (25)

Similar Records

Related Subjects