Highly Perfluorinated Covalent Triazine Frameworks Derived from&nbsp;a Low-Temperature Ionothermal&nbsp;Approach Towards Enhanced&nbsp;CO2 Electroreduction

Suo, Xian; Zhang, Fengtao; Yang, Zhenzhen; Chen, Hao; Wang, Tao; Wang, Zongyu; Kobayashi, Takeshi; Do-Thanh, Chi-Linh; Maltsev, Dmitry; Liu, Zhimin; Dai, Sheng

doi:10.1002/anie.202109342

Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO₂ Electroreduction

Journal Article · Tue Sep 28 04:00:00 EDT 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202109342· OSTI ID:1827100

Suo, Xian ^[1]; Zhang, Fengtao ^[2]; ^[3]; Chen, Hao ^[1]; ^[3]; ^[3]; Kobayashi, Takeshi ^[4]; Do-Thanh, Chi-Linh ^[1]; ^[1]; Liu, Zhimin ^[2]; ^[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)

Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-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 1.1 nm. 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.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1827100

Alternate ID(s):: OSTI ID: 1844851

Report Number(s):: IS-J--10,605

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 49 Vol. 60; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Rational Extension of the Family of Layered, Covalent, Triazine-Based Frameworks with Regular Porosity Bojdys, Michael J.; Jeromenok, Jekaterina; Thomas, Arne Advanced Materials, Vol. 22, Issue 19 https://doi.org/10.1002/adma.200903436	journal	March 2010
Porous, Fluorescent, Covalent Triazine-Based Frameworks Via Room-Temperature and Microwave-Assisted Synthesis Ren, Shijie; Bojdys, Michael J.; Dawson, Robert Advanced Materials, Vol. 24, Issue 17 https://doi.org/10.1002/adma.201200751	journal	April 2012
Metal-Free Carbon Materials for CO ₂ Electrochemical Reduction Duan, Xiaochuan; Xu, Jiantie; Wei, Zengxi Advanced Materials, Vol. 29, Issue 41 https://doi.org/10.1002/adma.201701784	journal	September 2017
New Layered Triazine Framework/Exfoliated 2D Polymer with Superior Sodium-Storage Properties Liu, Jingjing; Lyu, Pengbo; Zhang, Yu Advanced Materials, Vol. 30, Issue 11 https://doi.org/10.1002/adma.201705401	journal	January 2018
Corrected Horváth-Kawazoe equations for pore-size distribution Rege, Salil U.; Yang, Ralph T. AIChE Journal, Vol. 46, Issue 4 https://doi.org/10.1002/aic.690460408	journal	April 2000
Ionothermalsynthese von porösen kovalenten Triazin- Polymernetzwerken Kuhn, Pierre; Antonietti, Markus; Thomas, Arne Angewandte Chemie, Vol. 120, Issue 18 https://doi.org/10.1002/ange.200705710	journal	April 2008
Enantioselective Enolate Protonations: Friedel-Crafts Reactions with α-Substituted Acrylates Sibi, Mukund P.; Coulomb, Julien; Stanley, Levi M. Angewandte Chemie, Vol. 120, Issue 51 https://doi.org/10.1002/ange.200804221	journal	December 2008
Metalltriflimidate sind bessere Katalysatoren für die organische Synthese als Metalltriflate - der Effekt eines stark delokalisierten Gegenions Antoniotti, Sylvain; Dalla, Vincent; Duñach, Elisabet Angewandte Chemie, Vol. 122, Issue 43 https://doi.org/10.1002/ange.200906407	journal	August 2010
Elemental-Sulfur-Mediated Facile Synthesis of a Covalent Triazine Framework for High-Performance Lithium-Sulfur Batteries Talapaneni, Siddulu Naidu; Hwang, Tae Hoon; Je, Sang Hyun Angewandte Chemie, Vol. 128, Issue 9 https://doi.org/10.1002/ange.201511553	journal	January 2016
Nanostrukturierte Materialien für die elektrokatalytische CO ₂ -Reduktion und ihre Reaktionsmechanismen Zhang, Lei; Zhao, Zhi-Jian; Gong, Jinlong Angewandte Chemie, Vol. 129, Issue 38 https://doi.org/10.1002/ange.201612214	journal	July 2017
Mechanochemical Friedel-Crafts Alkylation-A Sustainable Pathway Towards Porous Organic Polymers Troschke, Erik; Grätz, Sven; Lübken, Tilo Angewandte Chemie, Vol. 129, Issue 24 https://doi.org/10.1002/ange.201702303	journal	May 2017
Covalent Triazine Frameworks via a Low-Temperature Polycondensation Approach Wang, Kewei; Yang, Li-Ming; Wang, Xi Angewandte Chemie, Vol. 129, Issue 45 https://doi.org/10.1002/ange.201708548	journal	October 2017
Metal-Free Fluorine-Doped Carbon Electrocatalyst for CO ₂ Reduction Outcompeting Hydrogen Evolution Xie, Jiafang; Zhao, Xiaotao; Wu, Maoxiang Angewandte Chemie, Vol. 130, Issue 31 https://doi.org/10.1002/ange.201802055	journal	April 2018
Crystalline Covalent Triazine Frameworks by In Situ Oxidation of Alcohols to Aldehyde Monomers Liu, Manying; Huang, Qi; Wang, Shaolei Angewandte Chemie, Vol. 130, Issue 37 https://doi.org/10.1002/ange.201806664	journal	August 2018
Perfluorinated Covalent Triazine Framework Derived Hybrids for the Highly Selective Electroconversion of Carbon Dioxide into Methane Wang, Yuanshuang; Chen, Junxiang; Wang, Genxiang Angewandte Chemie, Vol. 130, Issue 40 https://doi.org/10.1002/ange.201807173	journal	September 2018
Lithium‐Salt Mediated Synthesis of a Covalent Triazine Framework for Highly Stable Lithium Metal Batteries Zhou, Tianhong; Zhao, Yan; Choi, Jang Wook Angewandte Chemie, Vol. 131, Issue 47 https://doi.org/10.1002/ange.201908513	journal	November 2019
Porous, Covalent Triazine-Based Frameworks Prepared by Ionothermal Synthesis Kuhn, Pierre; Antonietti, Markus; Thomas, Arne Angewandte Chemie International Edition, Vol. 47, Issue 18 https://doi.org/10.1002/anie.200705710	journal	April 2008
Enantioselective Enolate Protonations: Friedel-Crafts Reactions with α-Substituted Acrylates Sibi, Mukund P.; Coulomb, Julien; Stanley, Levi M. Angewandte Chemie International Edition, Vol. 47, Issue 51 https://doi.org/10.1002/anie.200804221	journal	December 2008
Metal Triflimidates: Better than Metal Triflates as Catalysts in Organic Synthesis-The Effect of a Highly Delocalized Counteranion Antoniotti, Sylvain; Dalla, Vincent; Duñach, Elisabet Angewandte Chemie International Edition, Vol. 49, Issue 43, p. 7860-7888 https://doi.org/10.1002/anie.200906407	journal	August 2010
Elemental-Sulfur-Mediated Facile Synthesis of a Covalent Triazine Framework for High-Performance Lithium-Sulfur Batteries Talapaneni, Siddulu Naidu; Hwang, Tae Hoon; Je, Sang Hyun Angewandte Chemie International Edition, Vol. 55, Issue 9 https://doi.org/10.1002/anie.201511553	journal	January 2016
Nanostructured Materials for Heterogeneous Electrocatalytic CO ₂ Reduction and their Related Reaction Mechanisms Zhang, Lei; Zhao, Zhi-Jian; Gong, Jinlong Angewandte Chemie International Edition, Vol. 56, Issue 38 https://doi.org/10.1002/anie.201612214	journal	July 2017
Mechanochemical Friedel-Crafts Alkylation-A Sustainable Pathway Towards Porous Organic Polymers Troschke, Erik; Grätz, Sven; Lübken, Tilo Angewandte Chemie International Edition, Vol. 56, Issue 24 https://doi.org/10.1002/anie.201702303	journal	May 2017
Covalent Triazine Frameworks via a Low-Temperature Polycondensation Approach Wang, Kewei; Yang, Li-Ming; Wang, Xi Angewandte Chemie International Edition, Vol. 56, Issue 45 https://doi.org/10.1002/anie.201708548	journal	October 2017
Metal-Free Fluorine-Doped Carbon Electrocatalyst for CO ₂ Reduction Outcompeting Hydrogen Evolution Xie, Jiafang; Zhao, Xiaotao; Wu, Maoxiang Angewandte Chemie International Edition, Vol. 57, Issue 31 https://doi.org/10.1002/anie.201802055	journal	April 2018
Crystalline Covalent Triazine Frameworks by In Situ Oxidation of Alcohols to Aldehyde Monomers Liu, Manying; Huang, Qi; Wang, Shaolei Angewandte Chemie International Edition, Vol. 57, Issue 37 https://doi.org/10.1002/anie.201806664	journal	August 2018
Perfluorinated Covalent Triazine Framework Derived Hybrids for the Highly Selective Electroconversion of Carbon Dioxide into Methane Wang, Yuanshuang; Chen, Junxiang; Wang, Genxiang Angewandte Chemie International Edition, Vol. 57, Issue 40 https://doi.org/10.1002/anie.201807173	journal	October 2018
Lithium‐Salt Mediated Synthesis of a Covalent Triazine Framework for Highly Stable Lithium Metal Batteries Zhou, Tianhong; Zhao, Yan; Choi, Jang Wook Angewandte Chemie International Edition, Vol. 58, Issue 47 https://doi.org/10.1002/anie.201908513	journal	November 2019
Covalent Triazine Frameworks as Heterogeneous Catalysts for the Synthesis of Cyclic and Linear Carbonates from Carbon Dioxide and Epoxides Roeser, Jérôme; Kailasam, Kamalakannan; Thomas, Arne ChemSusChem, Vol. 5, Issue 9 https://doi.org/10.1002/cssc.201200091	journal	August 2012
What Fluorine Can Do in CO ₂ Chemistry: Applications from Homogeneous to Heterogeneous Systems Chen, Hao; Yang, Zhenzhen; Do‐Thanh, Chi‐Linh ChemSusChem https://doi.org/10.1002/cssc.202001638	journal	August 2020
Efficient Preparation of Anhydrous Metallic Triflates and Triflimides under Ultrasonic Activation Legrave, Nathalie; Couhert, Audrey; Olivero, Sandra European Journal of Organic Chemistry, Vol. 2012, Issue 5 https://doi.org/10.1002/ejoc.201101686	journal	January 2012
Computer fitting of Voigt profiles to Raman lines Sundius, T. Journal of Raman Spectroscopy, Vol. 1, Issue 5 https://doi.org/10.1002/jrs.1250010506	journal	November 1973
Copper(II) bis((trifluoromethyl) sulfonyl) amide. A novel Lewis acid catalyst in Diels-Alder reactions of cyclopentadiene with methyl vinyl ketone Nie, Jin; Kobayashi, Hiroshi; Sonoda, Takaaki Catalysis Today, Vol. 36, Issue 1 https://doi.org/10.1016/S0920-5861(96)00199-X	journal	April 1997
Covalent Organic Frameworks Linked by Amine Bonding for Concerted Electrochemical Reduction of CO2 Liu, Haoyu; Chu, Jun; Yin, Zhenglei Chem, Vol. 4, Issue 7 https://doi.org/10.1016/j.chempr.2018.05.003	journal	July 2018
Opportunity of Atomically Thin Two-Dimensional Catalysts for Promoting CO ₂ Electroreduction Li, Xiaodong; Wang, Shumin; Li, Li Accounts of Chemical Research, Vol. 53, Issue 12 https://doi.org/10.1021/acs.accounts.0c00626	journal	November 2020
Carbon- and Nitrogen-Based Organic Frameworks Sakaushi, Ken; Antonietti, Markus Accounts of Chemical Research, Vol. 48, Issue 6 https://doi.org/10.1021/acs.accounts.5b00010	journal	May 2015
Covalent Triazine Frameworks as Emerging Heterogeneous Photocatalysts Qian, Zhuangfei; Wang, Zi Jun; Zhang, Kai A. I. Chemistry of Materials, Vol. 33, Issue 6 https://doi.org/10.1021/acs.chemmater.0c04348	journal	March 2021
Charged Covalent Triazine Frameworks for CO ₂ Capture and Conversion Buyukcakir, Onur; Je, Sang Hyun; Talapaneni, Siddulu Naidu ACS Applied Materials & Interfaces, Vol. 9, Issue 8 https://doi.org/10.1021/acsami.6b16769	journal	February 2017
Achieving Highly Efficient, Selective, and Stable CO ₂ Reduction on Nitrogen-Doped Carbon Nanotubes Wu, Jingjie; Yadav, Ram Manohar; Liu, Mingjie ACS Nano, Vol. 9, Issue 5 https://doi.org/10.1021/acsnano.5b01079	journal	April 2015
Covalent Triazine Frameworks Prepared from 1,3,5-Tricyanobenzene Katekomol, Phisan; Roeser, Jérôme; Bojdys, Michael Chemistry of Materials, Vol. 25, Issue 9 https://doi.org/10.1021/cm303751n	journal	April 2013
A Superacid-Catalyzed Synthesis of Porous Membranes Based on Triazine Frameworks for CO₂ Separation Zhu, Xiang; Tian, Chengcheng; Mahurin, Shannon M. Journal of the American Chemical Society, Vol. 134, Issue 25, p. 10478-10484 https://doi.org/10.1021/ja304879c	journal	June 2012
Structural Evolution of 2D Microporous Covalent Triazine-Based Framework toward the Study of High-Performance Supercapacitors Hao, Long; Ning, Jing; Luo, Bin Journal of the American Chemical Society, Vol. 137, Issue 1 https://doi.org/10.1021/ja508693y	journal	December 2014
From Microporous Regular Frameworks to Mesoporous Materials with Ultrahigh Surface Area: Dynamic Reorganization of Porous Polymer Networks Kuhn, Pierre; Forget, Aurélien; Su, Dangsheng Journal of the American Chemical Society, Vol. 130, Issue 40 https://doi.org/10.1021/ja803708s	journal	October 2008
Transformation Strategy for Highly Crystalline Covalent Triazine Frameworks: From Staggered AB to Eclipsed AA Stacking Yang, Zhenzhen; Chen, Hao; Wang, Song Journal of the American Chemical Society, Vol. 142, Issue 15 https://doi.org/10.1021/jacs.0c00365	journal	March 2020
In Situ Doping Strategy for the Preparation of Conjugated Triazine Frameworks Displaying Efficient CO ₂ Capture Performance Zhu, Xiang; Tian, Chengcheng; Veith, Gabriel M. Journal of the American Chemical Society, Vol. 138, Issue 36 https://doi.org/10.1021/jacs.6b07644	journal	September 2016
Solution Synthesis of Semiconducting Two-Dimensional Polymer via Trimerization of Carbonitrile Liu, Jingjing; Zan, Wu; Li, Ke Journal of the American Chemical Society, Vol. 139, Issue 34 https://doi.org/10.1021/jacs.7b05025	journal	July 2017
Triazine Functionalized Porous Covalent Organic Framework for Photo-organocatalytic E – Z Isomerization of Olefins Bhadra, Mohitosh; Kandambeth, Sharath; Sahoo, Manoj K. Journal of the American Chemical Society, Vol. 141, Issue 15 https://doi.org/10.1021/jacs.9b01891	journal	March 2019
Zn(II)-Catalyzed Synthesis of Piperidines from Propargyl Amines and Cyclopropanes Lebold, Terry P.; Leduc, Andrew B.; Kerr, Michael A. Organic Letters, Vol. 11, Issue 16 https://doi.org/10.1021/ol901435k	journal	August 2009
Net reduction of CO2 via its thermocatalytic and electrocatalytic transformation reactions in standard and hybrid processes Tackett, Brian M.; Gomez, Elaine; Chen, Jingguang G. Nature Catalysis, Vol. 2, Issue 5 https://doi.org/10.1038/s41929-019-0266-y	journal	April 2019
Metal bis{(trifluoromethyl)sulfonyl}amide complexes: highly efficient Friedel–Crafts acylation catalysts Earle, Martyn J.; Hakala, Ullastiina; McAuley, Barry J. Chem. Commun., Issue 12 https://doi.org/10.1039/B403650F	journal	January 2004
Electrocatalytic and homogeneous approaches to conversion of CO ₂ to liquid fuels Benson, Eric E.; Kubiak, Clifford P.; Sathrum, Aaron J. Chem. Soc. Rev., Vol. 38, Issue 1 https://doi.org/10.1039/B804323J	journal	January 2009
Targeted synthesis of a 3D porous aromatic framework for selective sorption of benzene Ren, Hao; Ben, Teng; Wang, Ensi Chem. Commun., Vol. 46, Issue 2 https://doi.org/10.1039/B914761F	journal	January 2010
A fluorine-containing hydrophobic covalent triazine framework with excellent selective CO ₂ capture performance Wang, Guangbo; Leus, Karen; Jena, Himanshu Sekhar Journal of Materials Chemistry A, Vol. 6, Issue 15 https://doi.org/10.1039/C7TA08913A	journal	January 2018
Covalent triazine frameworks: synthesis and applications Liu, Manying; Guo, Liping; Jin, Shangbin Journal of Materials Chemistry A, Vol. 7, Issue 10 https://doi.org/10.1039/C8TA12442F	journal	January 2019
Straightforward preparation of fluorinated covalent triazine frameworks with significantly enhanced carbon dioxide and hydrogen adsorption capacities Wang, Guangbo; Onyshchenko, Yuliia; De Geyter, Nathalie Dalton Transactions, Vol. 48, Issue 47 https://doi.org/10.1039/C9DT03701B	journal	January 2019
1D/2D nitrogen-doped carbon nanorod arrays/ultrathin carbon nanosheets: outstanding catalysts for the highly efficient electroreduction of CO ₂ to CO Zhu, Ying; Lv, Kuilin; Wang, Xingpu Journal of Materials Chemistry A, Vol. 7, Issue 24 https://doi.org/10.1039/C9TA02353D	journal	January 2019
Influence of fluorination on CO ₂ adsorption in materials derived from fluorinated covalent triazine framework precursors Yang, Zhenzhen; Wang, Song; Zhang, Zihao Journal of Materials Chemistry A, Vol. 7, Issue 29 https://doi.org/10.1039/C9TA02573A	journal	January 2019
Covalent triazine frameworks for carbon dioxide capture Wang, Han; Jiang, Danni; Huang, Danlian Journal of Materials Chemistry A, Vol. 7, Issue 40 https://doi.org/10.1039/C9TA06847C	journal	January 2019
Covalent triazine framework/carbon nanotube hybrids enabling selective reduction of CO ₂ to CO at low overpotential Laemont, Andreas; Abednatanzi, Sara; Derakshandeh, Parviz Gohari Green Chemistry, Vol. 22, Issue 10 https://doi.org/10.1039/D0GC00090F	journal	January 2020
A perfluorinated covalent triazine-based framework for highly selective and water–tolerant CO2 capture Zhao, Yunfeng; Yao, Ke Xin; Teng, Baiyang Energy & Environmental Science, Vol. 6, Issue 12 https://doi.org/10.1039/c3ee42548g	journal	January 2013
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Organic semiconductor photocatalyst can bifunctionalize arenes and heteroarenes Ghosh, Indrajit; Khamrai, Jagadish; Savateev, Aleksandr Science, Vol. 365, Issue 6451 https://doi.org/10.1126/science.aaw3254	journal	July 2019
Recent Advancements in the Synthesis of Covalent Triazine Frameworks for Energy and Environmental Applications Zhang, Ying; Jin, Shangbin Polymers, Vol. 11, Issue 1 https://doi.org/10.3390/polym11010031	journal	December 2018

Similar Records

A highly proton conductive perfluorinated covalent triazine framework via low-temperature synthesis

Journal Article · Thu Dec 07 23:00:00 EST 2023 · Nature Communications · OSTI ID:2471476

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 electroreduction
Lewis superacid
covalent triazine framework
fluorinated
ionothermal procedure

Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction

Citation Formats

References (62)

Similar Records

Related Subjects

Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO₂ Electroreduction