Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction
Abstract
Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-the-art F-CTFs synthesized via the ZnCl2-promoted procedure have quite low fluorine contents due to C-F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400–700 °C). Fabricating F-CTFs with high fluorine contents (>30 wt %) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf2)2] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt %), surface area up to 367 m2 g-1, and micropores around 1.1nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO2 to CO, with faradaic efficiency of 95.7 % at -0.8 V and high current density (-141 mA cm-2) surpassing most of the metal-free electrocatalysts.
- Authors:
-
[3];
[3];
[3];
[1];
[5]
- Univ. of Tennessee, Knoxville, TN (United States)
- Chinese Academy of Sciences (CAS), Beijing (China)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Ames Lab., and Iowa State Univ., Ames, IA (United States)
- Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1827100
- Alternate Identifier(s):
- OSTI ID: 1844851
- Report Number(s):
- IS-J-10,605
Journal ID: ISSN 1433-7851
- Grant/Contract Number:
- AC02-07CH11358; AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 60; Journal Issue: 49; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; fluorinated; covalent triazine framework; Lewis superacid; ionothermal procedure; CO2 electroreduction
Citation Formats
Suo, Xian, Zhang, Fengtao, Yang, Zhenzhen, Chen, Hao, Wang, Tao, Wang, Zongyu, Kobayashi, Takeshi, Do-Thanh, Chi-Linh, Maltsev, Dmitry, Liu, Zhimin, and Dai, Sheng. Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction. United States: N. p., 2021.
Web. doi:10.1002/anie.202109342.
Suo, Xian, Zhang, Fengtao, Yang, Zhenzhen, Chen, Hao, Wang, Tao, Wang, Zongyu, Kobayashi, Takeshi, Do-Thanh, Chi-Linh, Maltsev, Dmitry, Liu, Zhimin, & Dai, Sheng. Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction. United States. https://doi.org/10.1002/anie.202109342
Suo, Xian, Zhang, Fengtao, Yang, Zhenzhen, Chen, Hao, Wang, Tao, Wang, Zongyu, Kobayashi, Takeshi, Do-Thanh, Chi-Linh, Maltsev, Dmitry, Liu, Zhimin, and Dai, Sheng. Tue .
"Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction". United States. https://doi.org/10.1002/anie.202109342. https://www.osti.gov/servlets/purl/1827100.
@article{osti_1827100,
title = {Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction},
author = {Suo, Xian and Zhang, Fengtao and Yang, Zhenzhen and Chen, Hao and Wang, Tao and Wang, Zongyu and Kobayashi, Takeshi and Do-Thanh, Chi-Linh and Maltsev, Dmitry and Liu, Zhimin and Dai, Sheng},
abstractNote = {Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-the-art F-CTFs synthesized via the ZnCl2-promoted procedure have quite low fluorine contents due to C-F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400–700 °C). Fabricating F-CTFs with high fluorine contents (>30 wt %) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf2)2] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt %), surface area up to 367 m2 g-1, and micropores around 1.1nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO2 to CO, with faradaic efficiency of 95.7 % at -0.8 V and high current density (-141 mA cm-2) surpassing most of the metal-free electrocatalysts.},
doi = {10.1002/anie.202109342},
journal = {Angewandte Chemie (International Edition)},
number = 49,
volume = 60,
place = {United States},
year = {Tue Sep 28 00:00:00 EDT 2021},
month = {Tue Sep 28 00:00:00 EDT 2021}
}
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Works referenced in this record:
Influence of fluorination on CO 2 adsorption in materials derived from fluorinated covalent triazine framework precursors
journal, January 2019
- Yang, Zhenzhen; Wang, Song; Zhang, Zihao
- Journal of Materials Chemistry A, Vol. 7, Issue 29
Nanostrukturierte Materialien für die elektrokatalytische CO 2 -Reduktion und ihre Reaktionsmechanismen
journal, July 2017
- Zhang, Lei; Zhao, Zhi-Jian; Gong, Jinlong
- Angewandte Chemie, Vol. 129, Issue 38
Corrected Horváth-Kawazoe equations for pore-size distribution
journal, April 2000
- Rege, Salil U.; Yang, Ralph T.
- AIChE Journal, Vol. 46, Issue 4
Perfluorinated Covalent Triazine Framework Derived Hybrids for the Highly Selective Electroconversion of Carbon Dioxide into Methane
journal, October 2018
- Wang, Yuanshuang; Chen, Junxiang; Wang, Genxiang
- Angewandte Chemie International Edition, Vol. 57, Issue 40
Transformation Strategy for Highly Crystalline Covalent Triazine Frameworks: From Staggered AB to Eclipsed AA Stacking
journal, March 2020
- Yang, Zhenzhen; Chen, Hao; Wang, Song
- Journal of the American Chemical Society, Vol. 142, Issue 15
Elemental-Sulfur-Mediated Facile Synthesis of a Covalent Triazine Framework for High-Performance Lithium-Sulfur Batteries
journal, January 2016
- Talapaneni, Siddulu Naidu; Hwang, Tae Hoon; Je, Sang Hyun
- Angewandte Chemie, Vol. 128, Issue 9
Mechanochemical Friedel-Crafts Alkylation-A Sustainable Pathway Towards Porous Organic Polymers
journal, May 2017
- Troschke, Erik; Grätz, Sven; Lübken, Tilo
- Angewandte Chemie, Vol. 129, Issue 24
Covalent triazine frameworks: synthesis and applications
journal, January 2019
- Liu, Manying; Guo, Liping; Jin, Shangbin
- Journal of Materials Chemistry A, Vol. 7, Issue 10
Computer fitting of Voigt profiles to Raman lines
journal, November 1973
- Sundius, T.
- Journal of Raman Spectroscopy, Vol. 1, Issue 5
Covalent Triazine Frameworks as Heterogeneous Catalysts for the Synthesis of Cyclic and Linear Carbonates from Carbon Dioxide and Epoxides
journal, August 2012
- Roeser, Jérôme; Kailasam, Kamalakannan; Thomas, Arne
- ChemSusChem, Vol. 5, Issue 9
Zn(II)-Catalyzed Synthesis of Piperidines from Propargyl Amines and Cyclopropanes
journal, August 2009
- Lebold, Terry P.; Leduc, Andrew B.; Kerr, Michael A.
- Organic Letters, Vol. 11, Issue 16
New Layered Triazine Framework/Exfoliated 2D Polymer with Superior Sodium-Storage Properties
journal, January 2018
- Liu, Jingjing; Lyu, Pengbo; Zhang, Yu
- Advanced Materials, Vol. 30, Issue 11
Covalent triazine frameworks for carbon dioxide capture
journal, January 2019
- Wang, Han; Jiang, Danni; Huang, Danlian
- Journal of Materials Chemistry A, Vol. 7, Issue 40
Charged Covalent Triazine Frameworks for CO 2 Capture and Conversion
journal, February 2017
- Buyukcakir, Onur; Je, Sang Hyun; Talapaneni, Siddulu Naidu
- ACS Applied Materials & Interfaces, Vol. 9, Issue 8
Metal-Free Fluorine-Doped Carbon Electrocatalyst for CO 2 Reduction Outcompeting Hydrogen Evolution
journal, April 2018
- Xie, Jiafang; Zhao, Xiaotao; Wu, Maoxiang
- Angewandte Chemie, Vol. 130, Issue 31
Lithium‐Salt Mediated Synthesis of a Covalent Triazine Framework for Highly Stable Lithium Metal Batteries
journal, November 2019
- Zhou, Tianhong; Zhao, Yan; Choi, Jang Wook
- Angewandte Chemie International Edition, Vol. 58, Issue 47
Mechanochemical Friedel-Crafts Alkylation-A Sustainable Pathway Towards Porous Organic Polymers
journal, May 2017
- Troschke, Erik; Grätz, Sven; Lübken, Tilo
- Angewandte Chemie International Edition, Vol. 56, Issue 24
Perfluorinated Covalent Triazine Framework Derived Hybrids for the Highly Selective Electroconversion of Carbon Dioxide into Methane
journal, September 2018
- Wang, Yuanshuang; Chen, Junxiang; Wang, Genxiang
- Angewandte Chemie, Vol. 130, Issue 40
Targeted synthesis of a 3D porous aromatic framework for selective sorption of benzene
journal, January 2010
- Ren, Hao; Ben, Teng; Wang, Ensi
- Chem. Commun., Vol. 46, Issue 2
A perfluorinated covalent triazine-based framework for highly selective and water–tolerant CO2 capture
journal, January 2013
- Zhao, Yunfeng; Yao, Ke Xin; Teng, Baiyang
- Energy & Environmental Science, Vol. 6, Issue 12
Copper(II) bis((trifluoromethyl) sulfonyl) amide. A novel Lewis acid catalyst in Diels-Alder reactions of cyclopentadiene with methyl vinyl ketone
journal, April 1997
- Nie, Jin; Kobayashi, Hiroshi; Sonoda, Takaaki
- Catalysis Today, Vol. 36, Issue 1
Opportunity of Atomically Thin Two-Dimensional Catalysts for Promoting CO 2 Electroreduction
journal, November 2020
- Li, Xiaodong; Wang, Shumin; Li, Li
- Accounts of Chemical Research, Vol. 53, Issue 12
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
A Superacid-Catalyzed Synthesis of Porous Membranes Based on Triazine Frameworks for CO2 Separation
journal, June 2012
- Zhu, Xiang; Tian, Chengcheng; Mahurin, Shannon M.
- Journal of the American Chemical Society, Vol. 134, Issue 25, p. 10478-10484
Ionothermalsynthese von porösen kovalenten Triazin- Polymernetzwerken
journal, April 2008
- Kuhn, Pierre; Antonietti, Markus; Thomas, Arne
- Angewandte Chemie, Vol. 120, Issue 18
From Microporous Regular Frameworks to Mesoporous Materials with Ultrahigh Surface Area: Dynamic Reorganization of Porous Polymer Networks
journal, October 2008
- Kuhn, Pierre; Forget, Aurélien; Su, Dangsheng
- Journal of the American Chemical Society, Vol. 130, Issue 40
Enantioselective Enolate Protonations: Friedel-Crafts Reactions with α-Substituted Acrylates
journal, December 2008
- Sibi, Mukund P.; Coulomb, Julien; Stanley, Levi M.
- Angewandte Chemie International Edition, Vol. 47, Issue 51
Efficient Preparation of Anhydrous Metallic Triflates and Triflimides under Ultrasonic Activation
journal, January 2012
- Legrave, Nathalie; Couhert, Audrey; Olivero, Sandra
- European Journal of Organic Chemistry, Vol. 2012, Issue 5
Solution Synthesis of Semiconducting Two-Dimensional Polymer via Trimerization of Carbonitrile
journal, July 2017
- Liu, Jingjing; Zan, Wu; Li, Ke
- Journal of the American Chemical Society, Vol. 139, Issue 34
Lithium‐Salt Mediated Synthesis of a Covalent Triazine Framework for Highly Stable Lithium Metal Batteries
journal, November 2019
- Zhou, Tianhong; Zhao, Yan; Choi, Jang Wook
- Angewandte Chemie, Vol. 131, Issue 47
Rational Extension of the Family of Layered, Covalent, Triazine-Based Frameworks with Regular Porosity
journal, March 2010
- Bojdys, Michael J.; Jeromenok, Jekaterina; Thomas, Arne
- Advanced Materials, Vol. 22, Issue 19
Elemental-Sulfur-Mediated Facile Synthesis of a Covalent Triazine Framework for High-Performance Lithium-Sulfur Batteries
journal, January 2016
- Talapaneni, Siddulu Naidu; Hwang, Tae Hoon; Je, Sang Hyun
- Angewandte Chemie International Edition, Vol. 55, Issue 9
Triazine Functionalized Porous Covalent Organic Framework for Photo-organocatalytic E – Z Isomerization of Olefins
journal, March 2019
- Bhadra, Mohitosh; Kandambeth, Sharath; Sahoo, Manoj K.
- Journal of the American Chemical Society, Vol. 141, Issue 15
Covalent Triazine Frameworks via a Low-Temperature Polycondensation Approach
journal, October 2017
- Wang, Kewei; Yang, Li-Ming; Wang, Xi
- Angewandte Chemie, Vol. 129, Issue 45
What Fluorine Can Do in CO 2 Chemistry: Applications from Homogeneous to Heterogeneous Systems
journal, August 2020
- Chen, Hao; Yang, Zhenzhen; Do‐Thanh, Chi‐Linh
- ChemSusChem
Covalent Organic Frameworks Linked by Amine Bonding for Concerted Electrochemical Reduction of CO2
journal, July 2018
- Liu, Haoyu; Chu, Jun; Yin, Zhenglei
- Chem, Vol. 4, Issue 7
Porous, Covalent Triazine-Based Frameworks Prepared by Ionothermal Synthesis
journal, April 2008
- Kuhn, Pierre; Antonietti, Markus; Thomas, Arne
- Angewandte Chemie International Edition, Vol. 47, Issue 18
Crystalline Covalent Triazine Frameworks by In Situ Oxidation of Alcohols to Aldehyde Monomers
journal, August 2018
- Liu, Manying; Huang, Qi; Wang, Shaolei
- Angewandte Chemie International Edition, Vol. 57, Issue 37
Metalltriflimidate sind bessere Katalysatoren für die organische Synthese als Metalltriflate - der Effekt eines stark delokalisierten Gegenions
journal, August 2010
- Antoniotti, Sylvain; Dalla, Vincent; Duñach, Elisabet
- Angewandte Chemie, Vol. 122, Issue 43
Nanostructured Materials for Heterogeneous Electrocatalytic CO 2 Reduction and their Related Reaction Mechanisms
journal, July 2017
- Zhang, Lei; Zhao, Zhi-Jian; Gong, Jinlong
- Angewandte Chemie International Edition, Vol. 56, Issue 38
Metal bis{(trifluoromethyl)sulfonyl}amide complexes: highly efficient Friedel–Crafts acylation catalysts
journal, January 2004
- Earle, Martyn J.; Hakala, Ullastiina; McAuley, Barry J.
- Chem. Commun., Issue 12
Net reduction of CO2 via its thermocatalytic and electrocatalytic transformation reactions in standard and hybrid processes
journal, April 2019
- Tackett, Brian M.; Gomez, Elaine; Chen, Jingguang G.
- Nature Catalysis, Vol. 2, Issue 5
Achieving Highly Efficient, Selective, and Stable CO 2 Reduction on Nitrogen-Doped Carbon Nanotubes
journal, April 2015
- Wu, Jingjie; Yadav, Ram Manohar; Liu, Mingjie
- ACS Nano, Vol. 9, Issue 5
Covalent Triazine Frameworks as Emerging Heterogeneous Photocatalysts
journal, March 2021
- Qian, Zhuangfei; Wang, Zi Jun; Zhang, Kai A. I.
- Chemistry of Materials, Vol. 33, Issue 6
In Situ Doping Strategy for the Preparation of Conjugated Triazine Frameworks Displaying Efficient CO 2 Capture Performance
journal, September 2016
- Zhu, Xiang; Tian, Chengcheng; Veith, Gabriel M.
- Journal of the American Chemical Society, Vol. 138, Issue 36
Recent Advancements in the Synthesis of Covalent Triazine Frameworks for Energy and Environmental Applications
journal, December 2018
- Zhang, Ying; Jin, Shangbin
- Polymers, Vol. 11, Issue 1
Metal Triflimidates: Better than Metal Triflates as Catalysts in Organic Synthesis-The Effect of a Highly Delocalized Counteranion
journal, August 2010
- Antoniotti, Sylvain; Dalla, Vincent; Duñach, Elisabet
- Angewandte Chemie International Edition, Vol. 49, Issue 43, p. 7860-7888
Structural Evolution of 2D Microporous Covalent Triazine-Based Framework toward the Study of High-Performance Supercapacitors
journal, December 2014
- Hao, Long; Ning, Jing; Luo, Bin
- Journal of the American Chemical Society, Vol. 137, Issue 1
Covalent Triazine Frameworks via a Low-Temperature Polycondensation Approach
journal, October 2017
- Wang, Kewei; Yang, Li-Ming; Wang, Xi
- Angewandte Chemie International Edition, Vol. 56, Issue 45
Metal-Free Carbon Materials for CO 2 Electrochemical Reduction
journal, September 2017
- Duan, Xiaochuan; Xu, Jiantie; Wei, Zengxi
- Advanced Materials, Vol. 29, Issue 41
Organic semiconductor photocatalyst can bifunctionalize arenes and heteroarenes
journal, July 2019
- Ghosh, Indrajit; Khamrai, Jagadish; Savateev, Aleksandr
- Science, Vol. 365, Issue 6451
A fluorine-containing hydrophobic covalent triazine framework with excellent selective CO 2 capture performance
journal, January 2018
- Wang, Guangbo; Leus, Karen; Jena, Himanshu Sekhar
- Journal of Materials Chemistry A, Vol. 6, Issue 15
Enantioselective Enolate Protonations: Friedel-Crafts Reactions with α-Substituted Acrylates
journal, December 2008
- Sibi, Mukund P.; Coulomb, Julien; Stanley, Levi M.
- Angewandte Chemie, Vol. 120, Issue 51
Electrocatalytic and homogeneous approaches to conversion of CO 2 to liquid fuels
journal, January 2009
- Benson, Eric E.; Kubiak, Clifford P.; Sathrum, Aaron J.
- Chem. Soc. Rev., Vol. 38, Issue 1
Metal-Free Fluorine-Doped Carbon Electrocatalyst for CO 2 Reduction Outcompeting Hydrogen Evolution
journal, April 2018
- Xie, Jiafang; Zhao, Xiaotao; Wu, Maoxiang
- Angewandte Chemie International Edition, Vol. 57, Issue 31
Porous, Fluorescent, Covalent Triazine-Based Frameworks Via Room-Temperature and Microwave-Assisted Synthesis
journal, April 2012
- Ren, Shijie; Bojdys, Michael J.; Dawson, Robert
- Advanced Materials, Vol. 24, Issue 17
Covalent triazine framework/carbon nanotube hybrids enabling selective reduction of CO 2 to CO at low overpotential
journal, January 2020
- Laemont, Andreas; Abednatanzi, Sara; Derakshandeh, Parviz Gohari
- Green Chemistry, Vol. 22, Issue 10
Crystalline Covalent Triazine Frameworks by In Situ Oxidation of Alcohols to Aldehyde Monomers
journal, August 2018
- Liu, Manying; Huang, Qi; Wang, Shaolei
- Angewandte Chemie, Vol. 130, Issue 37
Carbon- and Nitrogen-Based Organic Frameworks
journal, May 2015
- Sakaushi, Ken; Antonietti, Markus
- Accounts of Chemical Research, Vol. 48, Issue 6
Covalent Triazine Frameworks Prepared from 1,3,5-Tricyanobenzene
journal, April 2013
- Katekomol, Phisan; Roeser, Jérôme; Bojdys, Michael
- Chemistry of Materials, Vol. 25, Issue 9