Pyrolyzed Triazine-Based Nanoporous Frameworks Enable Electrochemical CO2 Reduction in Water

Zhu, Xiang; Tian, Chengcheng; Wu, Haihong; He, Yanyan; He, Lin; Wang, Hai; Zhuang, Xiaodong; Liu, Honglai; Xia, Chungu; Dai, Sheng

doi:10.1021/acsami.8b13110

Title: Pyrolyzed Triazine-Based Nanoporous Frameworks Enable Electrochemical CO₂ Reduction in Water

Journal Article · 28 November 2018 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.8b13110 · OSTI ID:1494879

^[1]; Tian, Chengcheng ^[2]; Wu, Haihong ^[3]; He, Yanyan ^[4]; He, Lin ^[3];

^[5];

^[6];

^[4]; Xia, Chungu ^[3];

^[2]

Chinese Academy of Sciences (CAS), Lanzhou (China). State Key Lab. for Oxo Synthesis and Selective Oxidation, Suzhou Research Inst. of Lanzhou Inst. of Chemical Physics; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Chinese Academy of Sciences (CAS), Lanzhou (China). State Key Lab. for Oxo Synthesis and Selective Oxidation, Suzhou Research Inst. of Lanzhou Inst. of Chemical Physics
East China Univ. of Science and Technology, Shanghai (China). School of Chemistry and Chemical Engineering
Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry
Shanghai Jiao Tong Univ., Shanghai (China). School of Chemistry and Chemical Engineering

The first study of rational synthesis of triazine-based nanoporous frameworks as electrocatalysts for CO₂ reduction reaction (CO₂RR) was presented. The resulting optimized framework with rich pyridinic nitrogen-containing sites can selectively reduce CO₂ to CO in water with a high Faradic efficiency of ca. 82% under a moderate overpotential of 560 mV. The key of our success lies in the use of pyridine-based backbones as sacrificial groups inside the triazine framework for in situ generation of CO₂RR-active pyridinic N-doped sites during the high-temperature ZnCl₂-promoted polymerization process. We anticipate that this study may facilitate new possibilities for the development of porous organic polymers for electrochemical conversion of CO₂.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1494879

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 50 Vol. 10; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

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
Bottom-Up Construction of Triazine-Based Frameworks as Metal-Free Electrocatalysts for Oxygen Reduction Reaction Hao, Long; Zhang, Shuangshuang; Liu, Rongji Advanced Materials, Vol. 27, Issue 20 https://doi.org/10.1002/adma.201500863	journal	April 2015
Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction of Carbon Dioxide Zhu, Dong Dong; Liu, Jin Long; Qiao, Shi Zhang Advanced Materials, Vol. 28, Issue 18 https://doi.org/10.1002/adma.201504766	journal	March 2016
Covalent Organic Frameworks for CO ₂ Capture Zeng, Yongfei; Zou, Ruqiang; Zhao, Yanli Advanced Materials, Vol. 28, Issue 15 https://doi.org/10.1002/adma.201505004	journal	February 2016
Porous Organic Polymers for Post-Combustion Carbon Capture Zou, Lanfang; Sun, Yujia; Che, Sai Advanced Materials, Vol. 29, Issue 37 https://doi.org/10.1002/adma.201700229	journal	July 2017
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
In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co ₄ N Hybrid for Highly Efficient Oxygen Evolution Zhu, Xiang; Jin, Tian; Tian, Chengcheng Advanced Materials, Vol. 29, Issue 47 https://doi.org/10.1002/adma.201704091	journal	October 2017
Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon-Based Catalysts for the Electrochemical Reduction of CO ₂ Vasileff, Anthony; Zheng, Yao; Qiao, Shi Zhang Advanced Energy Materials, Vol. 7, Issue 21 https://doi.org/10.1002/aenm.201700759	journal	July 2017
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
Compact Coupled Graphene and Porous Polyaryltriazine-Derived Frameworks as High Performance Cathodes for Lithium-Ion Batteries Su, Yuezeng; Liu, Yuxin; Liu, Ping Angewandte Chemie International Edition, Vol. 54, Issue 6 https://doi.org/10.1002/anie.201410154	journal	December 2014
Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO ₂ Electroreduction to CO and Hydrocarbons Varela, Ana Sofia; Ranjbar Sahraie, Nastaran; Steinberg, Julian Angewandte Chemie International Edition, Vol. 54, Issue 37 https://doi.org/10.1002/anie.201502099	journal	July 2015
Copper-Modified Covalent Triazine Frameworks as Non-Noble-Metal Electrocatalysts for Oxygen Reduction Iwase, Kazuyuki; Yoshioka, Tatsuro; Nakanishi, Shuji Angewandte Chemie International Edition, Vol. 54, Issue 38 https://doi.org/10.1002/anie.201503637	journal	July 2015
Nitrogen-Doped Carbon Nanotube Arrays for High-Efficiency Electrochemical Reduction of CO ₂ : On the Understanding of Defects, Defect Density, and Selectivity Sharma, Pranav P.; Wu, Jingjie; Yadav, Ram Manohar Angewandte Chemie International Edition, Vol. 54, Issue 46 https://doi.org/10.1002/anie.201506062	journal	September 2015
Metal-Free Nitrogen-Doped Mesoporous Carbon for Electroreduction of CO ₂ to Ethanol Song, Yanfang; Chen, Wei; Zhao, Chengcheng Angewandte Chemie International Edition, Vol. 56, Issue 36 https://doi.org/10.1002/anie.201706777	journal	July 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
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
Covalent Triazine-based Frameworks-Tailor-made Catalysts and Catalyst Supports for Molecular and Nanoparticulate Species Artz, Jens ChemCatChem, Vol. 10, Issue 8 https://doi.org/10.1002/cctc.201701820	journal	March 2018
Defect Engineering in Polymeric Cobalt Phthalocyanine Networks for Enhanced Electrochemical CO ₂ Reduction Wu, Haihong; Zeng, Min; Zhu, Xiang ChemElectroChem, Vol. 5, Issue 19 https://doi.org/10.1002/celc.201800806	journal	July 2018
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
Selective Aerobic Oxidation of HMF to 2,5-Diformylfuran on Covalent Triazine Frameworks-Supported Ru Catalysts Artz, Jens; Mallmann, Sabrina; Palkovits, Regina ChemSusChem, Vol. 8, Issue 4 https://doi.org/10.1002/cssc.201403078	journal	January 2015
Efficient production of hydrogen from formic acid using a Covalent Triazine Framework supported molecular catalyst Bavykina, A. V.; Goesten, M. G.; Kapteijn, F. ChemSusChem, Vol. 8, Issue 5 https://doi.org/10.1002/cssc.201403173	journal	February 2015
Supported Cobalt Polyphthalocyanine for High-Performance Electrocatalytic CO2 Reduction Han, Na; Wang, Yu; Ma, Lu Chem, Vol. 3, Issue 4 https://doi.org/10.1016/j.chempr.2017.08.002	journal	October 2017
Fundamentals and Challenges of Electrochemical CO2 Reduction Using Two-Dimensional Materials Sun, Zhenyu; Ma, Tao; Tao, Hengcong Chem, Vol. 3, Issue 4 https://doi.org/10.1016/j.chempr.2017.09.009	journal	October 2017
1,4-Phenylenediamine based covalent triazine framework as an electro catalyst Gopi, Sivalingam; Kathiresan, Murugavel Polymer, Vol. 109 https://doi.org/10.1016/j.polymer.2016.12.052	journal	January 2017
Nitrogen-Rich Covalent Triazine Frameworks as High-Performance Platforms for Selective Carbon Capture and Storage Hug, Stephan; Stegbauer, Linus; Oh, Hyunchul Chemistry of Materials, Vol. 27, Issue 23 https://doi.org/10.1021/acs.chemmater.5b03330	journal	November 2015
Porous Organic Materials: Strategic Design and Structure–Function Correlation Das, Saikat; Heasman, Patrick; Ben, Teng Chemical Reviews, Vol. 117, Issue 3 https://doi.org/10.1021/acs.chemrev.6b00439	journal	December 2016
Incorporation of Nitrogen Defects for Efficient Reduction of CO ₂ via Two-Electron Pathway on Three-Dimensional Graphene Foam Wu, Jingjie; Liu, Mingjie; Sharma, Pranav P. Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b04123	journal	December 2015
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
Selective Reduction of Nitrate by a Local Cell Catalyst Composed of Metal-Doped Covalent Triazine Frameworks Kamiya, Kazuhide; Tatebe, Tomomi; Yamamura, Shuhei ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.7b04465	journal	February 2018
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
Design and Preparation of Porous Polymers Wu, Dingcai; Xu, Fei; Sun, Bin Chemical Reviews, Vol. 112, Issue 7 https://doi.org/10.1021/cr200440z	journal	April 2012
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
Nitrogen-Based Catalysts for the Electrochemical Reduction of CO ₂ to CO Tornow, Claire E.; Thorson, Michael R.; Ma, Sichao Journal of the American Chemical Society, Vol. 134, Issue 48 https://doi.org/10.1021/ja308217w	journal	November 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
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
Exclusive Ni–N ₄ Sites Realize Near-Unity CO Selectivity for Electrochemical CO ₂ Reduction Li, Xiaogang; Bi, Wentuan; Chen, Minglong Journal of the American Chemical Society, Vol. 139, Issue 42 https://doi.org/10.1021/jacs.7b09074	journal	October 2017
Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction Diercks, Christian S.; Lin, Song; Kornienko, Nikolay Journal of the American Chemical Society, Vol. 140, Issue 3 https://doi.org/10.1021/jacs.7b11940	journal	January 2018
Design of Single-Atom Co–N ₅ Catalytic Site: A Robust Electrocatalyst for CO ₂ Reduction with Nearly 100% CO Selectivity and Remarkable Stability Pan, Yuan; Lin, Rui; Chen, Yinjuan Journal of the American Chemical Society, Vol. 140, Issue 12 https://doi.org/10.1021/jacs.8b00814	journal	February 2018
Toward Tailorable Porous Organic Polymer Networks: A High-Temperature Dynamic Polymerization Scheme Based on Aromatic Nitriles Kuhn, Pierre; Thomas, Arne; Antonietti, Markus Macromolecules, Vol. 42, Issue 1 https://doi.org/10.1021/ma802322j	journal	January 2009
Covalent Triazine Framework as Catalytic Support for Liquid Phase Reaction Chan-Thaw, Carine E.; Villa, Alberto; Katekomol, Phisan Nano Letters, Vol. 10, Issue 2 https://doi.org/10.1021/nl904082k	journal	February 2010
Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction Yang, Hong Bin; Hung, Sung-Fu; Liu, Song Nature Energy, Vol. 3, Issue 2 https://doi.org/10.1038/s41560-017-0078-8	journal	February 2018
The role of reticular chemistry in the design of CO2 reduction catalysts Diercks, Christian S.; Liu, Yuzhong; Cordova, Kyle E. Nature Materials, Vol. 17, Issue 4 https://doi.org/10.1038/s41563-018-0033-5	journal	February 2018
Functional porous organic polymers for heterogeneous catalysis Zhang, Yugen; Riduan, Siti Nurhanna Chem. Soc. Rev., Vol. 41, Issue 6 https://doi.org/10.1039/C1CS15227K	journal	January 2012
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
Covalent-organic frameworks: potential host materials for sulfur impregnation in lithium–sulfur batteries Liao, Huaping; Ding, Huimin; Li, Bijian J. Mater. Chem. A, Vol. 2, Issue 23 https://doi.org/10.1039/C4TA00523F	journal	January 2014
Hollow nanoporous covalent triazine frameworks via acid vapor-assisted solid phase synthesis for enhanced visible light photoactivity Huang, Wei; Wang, Zi Jun; Ma, Beatriz Chiyin Journal of Materials Chemistry A, Vol. 4, Issue 20 https://doi.org/10.1039/C6TA01828A	journal	January 2016
A photoluminescent covalent triazine framework: CO ₂ adsorption, light-driven hydrogen evolution and sensing of nitroaromatics Bhunia, Asamanjoy; Esquivel, Dolores; Dey, Subarna Journal of Materials Chemistry A, Vol. 4, Issue 35 https://doi.org/10.1039/C6TA04623A	journal	January 2016
Triazine-based covalent organic polymers: design, synthesis and applications in heterogeneous catalysis Puthiaraj, Pillaiyar; Lee, Yu-Ri; Zhang, Siqian Journal of Materials Chemistry A, Vol. 4, Issue 42 https://doi.org/10.1039/C6TA06089G	journal	January 2016
Two linkers are better than one: enhancing CO ₂ capture and separation with porous covalent triazine-based frameworks from mixed nitrile linkers Dey, Subarna; Bhunia, Asamanjoy; Breitzke, Hergen Journal of Materials Chemistry A, Vol. 5, Issue 7 https://doi.org/10.1039/C6TA07076K	journal	January 2017
Trends and challenges for microporous polymers Chaoui, Nicolas; Trunk, Matthias; Dawson, Robert Chemical Society Reviews, Vol. 46, Issue 11 https://doi.org/10.1039/C7CS00071E	journal	January 2017
Isolated Ni single atoms in graphene nanosheets for high-performance CO ₂ reduction Jiang, Kun; Siahrostami, Samira; Zheng, Tingting Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C7EE03245E	journal	January 2018
From covalent triazine-based frameworks to N-doped porous carbon/reduced graphene oxide nanosheets: efficient electrocatalysts for oxygen reduction Jiao, Long; Hu, Yingli; Ju, Huanxin Journal of Materials Chemistry A, Vol. 5, Issue 44 https://doi.org/10.1039/C7TA07387A	journal	January 2017
Covalent triazine framework modified with coordinatively-unsaturated Co or Ni atoms for CO ₂ electrochemical reduction Su, Panpan; Iwase, Kazuyuki; Harada, Takashi Chemical Science, Vol. 9, Issue 16 https://doi.org/10.1039/C8SC00604K	journal	January 2018
Conjugated microporous polymers: design, synthesis and application Xu, Yanhong; Jin, Shangbin; Xu, Hong Chemical Society Reviews, Vol. 42, Issue 20 https://doi.org/10.1039/c3cs60160a	journal	January 2013
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
Function-led design of new porous materials Slater, A. G.; Cooper, A. I. Science, Vol. 348, Issue 6238 https://doi.org/10.1126/science.aaa8075	journal	May 2015
Covalent organic frameworks comprising cobalt porphyrins for catalytic CO ₂ reduction in water Lin, Song; Diercks, Christian S.; Zhang, Yue-Biao Science, Vol. 349, Issue 6253 https://doi.org/10.1126/science.aac8343	journal	August 2015
The atom, the molecule, and the covalent organic framework Diercks, Christian S.; Yaghi, Omar M. Science, Vol. 355, Issue 6328 https://doi.org/10.1126/science.aal1585	journal	March 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Pyrolyzed Triazine-Based Nanoporous Frameworks Enable Electrochemical CO₂ Reduction in Water