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

Guan, Lijiang; Guo, Zhaoqi; Zhou, Qi; Zhang, Jin; Cheng, Cheng; Wang, Shengyao; Zhu, Xiang; Dai, Sheng; Jin, Shangbin

doi:10.1038/s41467-023-43829-4

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

Journal Article · Fri Dec 08 04:00:00 EST 2023 · Nature Communications

DOI:https://doi.org/10.1038/s41467-023-43829-4· OSTI ID:2471476

Guan, Lijiang ^[1]; Guo, Zhaoqi ^[2]; Zhou, Qi ^[1]; Zhang, Jin ^[1]; Cheng, Cheng ^[1]; ^[3]; Zhu, Xiang ^[4]; ^[5]; ^[1]

Xi’an Jiaotong University, Shaanxi (China)
Northwest University, Xi’an, Shaanxi (China)
Huazhong Agricultural University, Wuhan (China)
Chinese Academy of Sciences, Lanzhou (China)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Proton-conducting materials are essential to the emerging hydrogen economy. Covalent triazine frameworks (CTFs) are promising proton-conducting materials at high temperatures but need more effective sites to strengthen interaction for proton carriers. However, their construction and design in a concise condition are still challenges. Herein, we show a low temperature approach to synthesize CTFs via a direct cyclotrimerization of aromatic aldehyde using ammonium iodide as facile nitrogen source. Among the CTFs, the perfluorinated CTF (CTF-TF) was successfully synthesized with much lower temperature ( ≤ 160 °C) and open-air atmosphere. Due to the additional hydrogen-bonding interaction between fluorine atoms and proton carriers (H₃PO₄), the CTF-TF achieves a proton conductivity of 1.82 × 10^-1 S cm^-1 at 150 °C after H₃PO₄ loading. Moreover, the CTF-TF can be readily integrated into mixed matrix membranes, displaying high proton conduction abilities and good mechanical strength. This work provides an alternative strategy for rational design of proton conducting media.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Natural Science Foundation of China; Key Project of Natural Science Basic Research Program of Shaanxi; Qin Chuangyuan cited high level innovation and entrepreneurship talent project

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2471476

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 14; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (61)

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
Controlling Monomer Feeding Rate to Achieve Highly Crystalline Covalent Triazine Frameworks Liu, Manying; Jiang, Kai; Ding, Xing Advanced Materials, Vol. 31, Issue 19 https://doi.org/10.1002/adma.201807865	journal	March 2019
Acetylene and Diacetylene Functionalized Covalent Triazine Frameworks as Metal‐Free Photocatalysts for Hydrogen Peroxide Production: A New Two‐Electron Water Oxidation Pathway Chen, Liang; Wang, Lei; Wan, Yangyang Advanced Materials, Vol. 32, Issue 2 https://doi.org/10.1002/adma.201904433	journal	November 2019
Weakly Humidity‐Dependent Proton‐Conducting COF Membranes Cao, Li; Wu, Hong; Cao, Yu Advanced Materials, Vol. 32, Issue 52 https://doi.org/10.1002/adma.202005565	journal	November 2020
Polarization Engineering of Covalent Triazine Frameworks for Highly Efficient Photosynthesis of Hydrogen Peroxide from Molecular Oxygen and Water Wu, Chongbei; Teng, Zhenyuan; Yang, Chao Advanced Materials, Vol. 34, Issue 28 https://doi.org/10.1002/adma.202110266	journal	June 2022
Covalent‐Organic Frameworks (COFs) as Proton Conductors Sahoo, Rupam; Mondal, Supriya; Pal, Shyam Chand Advanced Energy Materials, Vol. 11, Issue 39 https://doi.org/10.1002/aenm.202102300	journal	September 2021
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
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
Direct Synthesis of a Covalent Triazine-Based Framework from Aromatic Amides Yu, Soo-Young; Mahmood, Javeed; Noh, Hyuk-Jun Angewandte Chemie International Edition, Vol. 57, Issue 28 https://doi.org/10.1002/anie.201801128	journal	April 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
Combined Intrinsic and Extrinsic Proton Conduction in Robust Covalent Organic Frameworks for Hydrogen Fuel Cell Applications Yang, Yi; He, Xueyi; Zhang, Penghui Angewandte Chemie International Edition, Vol. 59, Issue 9 https://doi.org/10.1002/anie.201913802	journal	January 2020
Strong‐Base‐Assisted Synthesis of a Crystalline Covalent Triazine Framework with High Hydrophilicity via Benzylamine Monomer for Photocatalytic Water Splitting Zhang, Siquan; Cheng, Guang; Guo, Liping Angewandte Chemie International Edition, Vol. 59, Issue 15 https://doi.org/10.1002/anie.201914424	journal	February 2020
Ultrafast and Stable Proton Conduction in Polybenzimidazole Covalent Organic Frameworks via Confinement and Activation Li, Juan; Wang, Jing; Wu, Zhenzhen Angewandte Chemie International Edition, Vol. 60, Issue 23 https://doi.org/10.1002/anie.202101400	journal	April 2021
Surface‐Mediated Construction of an Ultrathin Free‐Standing Covalent Organic Framework Membrane for Efficient Proton Conduction Liu, Lin; Yin, Liying; Cheng, Dongming Angewandte Chemie International Edition, Vol. 60, Issue 27 https://doi.org/10.1002/anie.202104106	journal	May 2021
Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low‐Temperature Ionothermal Approach Towards Enhanced CO ₂ Electroreduction Suo, Xian; Zhang, Fengtao; Yang, Zhenzhen Angewandte Chemie International Edition, Vol. 60, Issue 49 https://doi.org/10.1002/anie.202109342	journal	October 2021
Ionothermal Synthesis of Covalent Triazine Frameworks in a NaCl‐KCl‐ZnCl₂Eutectic Salt for the Hydrogen Evolution Reaction Lan, Zhi‐An; Wu, Meng; Fang, Zhongpu Angewandte Chemie International Edition, Vol. 61, Issue 18 https://doi.org/10.1002/anie.202201482	journal	March 2022
Tuning the Interlayer Interactions of 2D Covalent Organic Frameworks Enables an Ultrastable Platform for Anhydrous Proton Transport Jiang, Guoxing; Zou, Wenwu; Ou, Zhaoyuan Angewandte Chemie International Edition, Vol. 61, Issue 35 https://doi.org/10.1002/anie.202208086	journal	July 2022
Pore Geometry and Surface Engineering of Covalent Organic Frameworks for Anhydrous Proton Conduction Hao, Liqin; Jia, Shuping; Qiao, Xueling Angewandte Chemie International Edition, Vol. 62, Issue 6 https://doi.org/10.1002/anie.202217240	journal	December 2022
A Covalent Triazine‐Based Framework Consisting of Donor–Acceptor Dyads for Visible‐Light‐Driven Photocatalytic CO ₂ Reduction Zhong, Hong; Hong, Zixiao; Yang, Can ChemSusChem, Vol. 12, Issue 19 https://doi.org/10.1002/cssc.201901997	journal	September 2019
Construction of Fluorine‐ and Piperazine‐Engineered Covalent Triazine Frameworks Towards Enhanced Dual‐Ion Positive Electrode Performance Wang, Tao; Gaugler, James Anthony; Li, Meijia ChemSusChem, Vol. 16, Issue 4 https://doi.org/10.1002/cssc.202201219	journal	September 2022
Hydrogen Bond Activation by Pyridinic Nitrogen for the High Proton Conductivity of Covalent Triazine Framework Loaded with H₃PO₄ Liu, Manying; Deng, Wei‐Hua; Wang, Xueqing ChemSusChem, Vol. 15, Issue 23 https://doi.org/10.1002/cssc.202201298	journal	November 2022
Multiwfn: A multifunctional wavefunction analyzer Lu, Tian; Chen, Feiwu Journal of Computational Chemistry, Vol. 33, Issue 5 https://doi.org/10.1002/jcc.22885	journal	December 2011
Computational chemistry and molecular simulations of phosphoric acid Li, Shuo; Fried, J. R.; Sauer, Jeremy International Journal of Quantum Chemistry, Vol. 111, Issue 12 https://doi.org/10.1002/qua.22702	journal	September 2010
Software update: The ORCA program system—Version 5.0 Neese, Frank WIREs Computational Molecular Science, Vol. 12, Issue 5 https://doi.org/10.1002/wcms.1606	journal	March 2022
VMD: Visual molecular dynamics Humphrey, William; Dalke, Andrew; Schulten, Klaus Journal of Molecular Graphics, Vol. 14, Issue 1 https://doi.org/10.1016/0263-7855(96)00018-5	journal	February 1996
Proton conductive covalent organic frameworks Guo, Zhong-Cheng; Shi, Zhi-Qiang; Wang, Xin-Yue Coordination Chemistry Reviews, Vol. 422 https://doi.org/10.1016/j.ccr.2020.213465	journal	November 2020
Surpassing Robeson Upper Limit for CO2/N2 Separation with Fluorinated Carbon Molecular Sieve Membranes Yang, Zhenzhen; Guo, Wei; Mahurin, Shannon Mark Chem, Vol. 6, Issue 3 https://doi.org/10.1016/j.chempr.2019.12.006	journal	March 2020
Phosphoric acid-loaded covalent triazine framework for enhanced the proton conductivity of the proton exchange membrane Sun, Xiang; Song, Jun-Hua; Ren, Hong-qian Electrochimica Acta, Vol. 331 https://doi.org/10.1016/j.electacta.2019.135235	journal	January 2020
A review of high-temperature proton exchange membrane fuel cell (HT-PEMFC) system Rosli, R. E.; Sulong, A. B.; Daud, W. R. W. International Journal of Hydrogen Energy, Vol. 42, Issue 14 https://doi.org/10.1016/j.ijhydene.2016.06.211	journal	April 2017
Recent approaches to improve Nafion performance for fuel cell applications: A review Karimi, Mohammad Bagher; Mohammadi, Fereidoon; Hooshyari, Khadijeh International Journal of Hydrogen Energy, Vol. 44, Issue 54 https://doi.org/10.1016/j.ijhydene.2019.09.096	journal	November 2019
Proton exchange membranes for high temperature proton exchange membrane fuel cells: Challenges and perspectives Qu, Erli; Hao, Xiaofeng; Xiao, Min Journal of Power Sources, Vol. 533 https://doi.org/10.1016/j.jpowsour.2022.231386	journal	June 2022
Influence of ZIF-8 particle size in the performance of polybenzimidazole mixed matrix membranes for pre-combustion CO2 capture and its validation through interlaboratory test Sánchez-Laínez, Javier; Zornoza, Beatriz; Friebe, Sebastian Journal of Membrane Science, Vol. 515 https://doi.org/10.1016/j.memsci.2016.05.039	journal	October 2016
Mixed matrix proton exchange membranes for fuel cells: State of the art and perspectives Bakangura, Erigene; Wu, Liang; Ge, Liang Progress in Polymer Science, Vol. 57 https://doi.org/10.1016/j.progpolymsci.2015.11.004	journal	June 2016
In Situ-Doped Superacid in the Covalent Triazine Framework Membrane for Anhydrous Proton Conduction in a Wide Temperature Range from Subzero to Elevated Temperature Huang, Wenbo; Li, Bin; Wu, Yue ACS Applied Materials & Interfaces, Vol. 13, Issue 11 https://doi.org/10.1021/acsami.1c01134	journal	March 2021
Fluorinated, Sulfur-Rich, Covalent Triazine Frameworks for Enhanced Confinement of Polysulfides in Lithium–Sulfur Batteries Xu, Fei; Yang, Shuhao; Jiang, Guangshen ACS Applied Materials & Interfaces, Vol. 9, Issue 43 https://doi.org/10.1021/acsami.7b10991	journal	October 2017
Superprotonic Conduction of Acidified Benzimidazole-Linked Covalent Organic Framework Zhang, Jin; Kong, Ya-Ru; Liu, Yangyang ACS Materials Letters, Vol. 4, Issue 12 https://doi.org/10.1021/acsmaterialslett.2c00432	journal	November 2022
Few-Layered Fluorinated Triazine-Based Covalent Organic Nanosheets for High-Performance Alkali Organic Batteries Zhang, Hang; Sun, Weiwei; Chen, Xiudong ACS Nano, Vol. 13, Issue 12 https://doi.org/10.1021/acsnano.9b07360	journal	December 2019
Gas Adsorption Characterization of Ordered Organic−Inorganic Nanocomposite Materials Kruk, Michal; Jaroniec, Mietek Chemistry of Materials, Vol. 13, Issue 10 https://doi.org/10.1021/cm0101069	journal	October 2001
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
Perfluoroalkyl-Functionalized Covalent Organic Frameworks with Superhydrophobicity for Anhydrous Proton Conduction Wu, Xiaowei; Hong, You-lee; Xu, Bingqing Journal of the American Chemical Society, Vol. 142, Issue 33 https://doi.org/10.1021/jacs.0c06474	journal	July 2020
A Solid-State NMR Study of Hydrogen-Bonding Networks and Ion Dynamics in Benzimidazole Salts Traer, Jason W.; Britten, James F.; Goward, Gillian R. The Journal of Physical Chemistry B, Vol. 111, Issue 20 https://doi.org/10.1021/jp071471b	journal	May 2007
The mechanism of proton conduction in phosphoric acid Vilčiauskas, Linas; Tuckerman, Mark E.; Bester, Gabriel Nature Chemistry, Vol. 4, Issue 6 https://doi.org/10.1038/nchem.1329	journal	April 2012
Confining H3PO4 network in covalent organic frameworks enables proton super flow Tao, Shanshan; Zhai, Lipeng; Dinga Wonanke, A. D. Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15918-1	journal	April 2020
Thermochemical electronegativities of the elements Tantardini, Christian; Oganov, Artem R. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-22429-0	journal	April 2021
Tough, stable and self-healing luminescent perovskite-polymer matrix applicable to all harsh aquatic environments Liu, Yuncong; Chen, Tao; Jin, Zhekai Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-29084-z	journal	March 2022
Short hydrogen-bond network confined on COF surfaces enables ultrahigh proton conductivity Shi, Benbing; Pang, Xiao; Li, Shunning Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-33868-8	journal	November 2022
New anhydrous proton exchange membranes for high-temperature fuel cells based on PVDF–PVP blended polymers Guo, Zhibin; Xu, Xin; Xiang, Yan Journal of Materials Chemistry A, Vol. 3, Issue 1 https://doi.org/10.1039/C4TA04952G	journal	January 2015
Proton-conducting crystalline porous materials Meng, Xing; Wang, Hai-Ning; Song, Shu-Yan Chemical Society Reviews, Vol. 46, Issue 2 https://doi.org/10.1039/C6CS00528D	journal	January 2017
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
Advanced functional polymer materials Wang, Kaojin; Amin, Kamran; An, Zesheng Materials Chemistry Frontiers, Vol. 4, Issue 7 https://doi.org/10.1039/D0QM00025F	journal	January 2020
Atom-efficient synthesis of 2,4,6-trisubstituted 1,3,5-triazines via Fe-catalyzed cyclization of aldehydes with NH₄I as the sole nitrogen source Xiao, Jiang; Ren, Shuang; Liu, Qiang RSC Advances, Vol. 10, Issue 37 https://doi.org/10.1039/D0RA03323E	journal	January 2020
Post-synthetic modification of porous materials: superprotonic conductivities and membrane applications in fuel cells Kang, Dong Won; Kang, Minjung; Hong, Chang Seop Journal of Materials Chemistry A, Vol. 8, Issue 16 https://doi.org/10.1039/D0TA01733G	journal	January 2020
Single-crystal superprotonic conductivity in an interpenetrated hydrogen-bonded quadruplex framework Zhou, Mu-Yang; Wang, Hao-Yu; Wang, Zhi-Shuo Chemical Communications, Vol. 58, Issue 6 https://doi.org/10.1039/D1CC06004J	journal	January 2022
Construction of unimpeded proton-conducting pathways in solution-processed nanoporous polymer membranes Tang, Xiaohui; Ma, Nattapol; Xu, Hong Materials Horizons, Vol. 8, Issue 11 https://doi.org/10.1039/D1MH01147B	journal	January 2021
Construction of dense H-bond acceptors in the channels of covalent organic frameworks for proton conduction Liu, Sijia; Liu, Minghao; Li, Xuewen Journal of Materials Chemistry A, Vol. 11, Issue 26 https://doi.org/10.1039/D3TA01907A	journal	January 2023
Recent developments in proton exchange membranes for fuel cells Devanathan, Ram Energy & Environmental Science, Vol. 1, Issue 1 https://doi.org/10.1039/b808149m	journal	January 2008
Proton-conducting membranes based on benzimidazole polymers for high-temperature PEM fuel cells. A chemical quest Asensio, Juan Antonio; Sánchez, Eduardo M.; Gómez-Romero, Pedro Chemical Society Reviews, Vol. 39, Issue 8 https://doi.org/10.1039/b922650h	journal	January 2010
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
Electronegativity Identification of Novel Superhard Materials Li, Keyan; Wang, Xingtao; Zhang, Fangfang Physical Review Letters, Vol. 100, Issue 23 https://doi.org/10.1103/PhysRevLett.100.235504	journal	June 2008
Covalent organic framework–based porous ionomers for high-performance fuel cells Zhang, Qingnuan; Dong, Shuda; Shao, Pengpeng Science, Vol. 378, Issue 6616 https://doi.org/10.1126/science.abm6304	journal	October 2022
Conductivity of PBI Membranes for High-Temperature Polymer Electrolyte Fuel Cells Ma, Y. -L.; Wainright, J. S.; Litt, M. H. Journal of The Electrochemical Society, Vol. 151, Issue 1 https://doi.org/10.1149/1.1630037	journal	January 2004

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