Covalent Organic Framework (COF) Derived Ni–N–C Catalysts for Electrochemical CO 2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites
Abstract
Electrochemical CO2 reduction is a potential approach to convert CO2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel-nitrogen-doped carbon (Ni-N-C) is an efficient catalyst for CO2 reduction to CO, and the single-site Ni-Nx motif is believed to be the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)-derived Ni-N-C catalysts, for which the Ni-Nx content could be adjusted by the pyrolysis temperature. The combination of high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure evidenced the presence of Ni single-sites, and quantitative X-ray photoemission addressed the relation between active site density and turnover frequency.
- Authors:
-
[1];
[2];
[3];
[3];
[2];
[2];
[3];
[1];
[1]
- Technical Univ. of Berlin (Germany)
- Technical Univ. of Denmark, Lyngby (Denmark)
- Fritz-Haber Institute of Max-Planck Society, Berlin (Germany)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); European Union (EU); German Research Foundation (DFG)
- OSTI Identifier:
- 1867772
- Grant/Contract Number:
- AC05-00OR22725; 851441; 390540038
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 61; Journal Issue: 15; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; active site density; CO2 reduction; covalent organic framework; single-site Ni-N-C; turnover frequency
Citation Formats
Li, Changxia, Ju, Wen, Vijay, Sudarshan, Timoshenko, Janis, Mou, Kaiwen, Cullen, David A., Yang, Jin, Wang, Xingli, Pachfule, Pradip, Brückner, Sven, Jeon, Hyo Sang, Haase, Felix T., Tsang, Sze‐Chun, Rettenmaier, Clara, Chan, Karen, Cuenya, Beatriz Roldan, Thomas, Arne, and Strasser, Peter. Covalent Organic Framework (COF) Derived Ni–N–C Catalysts for Electrochemical CO 2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites. United States: N. p., 2022.
Web. doi:10.1002/anie.202114707.
Li, Changxia, Ju, Wen, Vijay, Sudarshan, Timoshenko, Janis, Mou, Kaiwen, Cullen, David A., Yang, Jin, Wang, Xingli, Pachfule, Pradip, Brückner, Sven, Jeon, Hyo Sang, Haase, Felix T., Tsang, Sze‐Chun, Rettenmaier, Clara, Chan, Karen, Cuenya, Beatriz Roldan, Thomas, Arne, & Strasser, Peter. Covalent Organic Framework (COF) Derived Ni–N–C Catalysts for Electrochemical CO 2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites. United States. https://doi.org/10.1002/anie.202114707
Li, Changxia, Ju, Wen, Vijay, Sudarshan, Timoshenko, Janis, Mou, Kaiwen, Cullen, David A., Yang, Jin, Wang, Xingli, Pachfule, Pradip, Brückner, Sven, Jeon, Hyo Sang, Haase, Felix T., Tsang, Sze‐Chun, Rettenmaier, Clara, Chan, Karen, Cuenya, Beatriz Roldan, Thomas, Arne, and Strasser, Peter. Mon .
"Covalent Organic Framework (COF) Derived Ni–N–C Catalysts for Electrochemical CO 2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites". United States. https://doi.org/10.1002/anie.202114707. https://www.osti.gov/servlets/purl/1867772.
@article{osti_1867772,
title = {Covalent Organic Framework (COF) Derived Ni–N–C Catalysts for Electrochemical CO 2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites},
author = {Li, Changxia and Ju, Wen and Vijay, Sudarshan and Timoshenko, Janis and Mou, Kaiwen and Cullen, David A. and Yang, Jin and Wang, Xingli and Pachfule, Pradip and Brückner, Sven and Jeon, Hyo Sang and Haase, Felix T. and Tsang, Sze‐Chun and Rettenmaier, Clara and Chan, Karen and Cuenya, Beatriz Roldan and Thomas, Arne and Strasser, Peter},
abstractNote = {Electrochemical CO2 reduction is a potential approach to convert CO2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel-nitrogen-doped carbon (Ni-N-C) is an efficient catalyst for CO2 reduction to CO, and the single-site Ni-Nx motif is believed to be the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)-derived Ni-N-C catalysts, for which the Ni-Nx content could be adjusted by the pyrolysis temperature. The combination of high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure evidenced the presence of Ni single-sites, and quantitative X-ray photoemission addressed the relation between active site density and turnover frequency.},
doi = {10.1002/anie.202114707},
journal = {Angewandte Chemie (International Edition)},
number = 15,
volume = 61,
place = {United States},
year = {Mon Jan 31 00:00:00 EST 2022},
month = {Mon Jan 31 00:00:00 EST 2022}
}
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Works referenced in this record:
Competition between CO 2 Reduction and Hydrogen Evolution on a Gold Electrode under Well-Defined Mass Transport Conditions
journal, February 2020
- Goyal, Akansha; Marcandalli, Giulia; Mints, Vladislav A.
- Journal of the American Chemical Society, Vol. 142, Issue 9
The chemical identity, state and structure of catalytically active centers during the electrochemical CO 2 reduction on porous Fe–nitrogen–carbon (Fe–N–C) materials
journal, January 2018
- Leonard, Nathaniel; Ju, Wen; Sinev, Ilya
- Chemical Science, Vol. 9, Issue 22
CO2 electrochemical catalytic reduction with a highly active cobalt phthalocyanine
journal, August 2019
- Wang, Min; Torbensen, Kristian; Salvatore, Danielle
- Nature Communications, Vol. 10, Issue 1
Uniformity Is Key in Defining Structure–Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO 2
journal, December 2019
- Resasco, Joaquin; DeRita, Leo; Dai, Sheng
- Journal of the American Chemical Society, Vol. 142, Issue 1
Molecular Nitrogen-Carbon Catalysts, Solid Metal Organic Framework Catalysts, and Solid Metal/Nitrogen-Doped Carbon (MNC) Catalysts for the Electrochemical CO 2 Reduction
journal, July 2018
- Varela, Ana Sofia; Ju, Wen; Strasser, Peter
- Advanced Energy Materials, Vol. 8, Issue 30
Establishing reactivity descriptors for platinum group metal (PGM)-free Fe–N–C catalysts for PEM fuel cells
journal, January 2020
- Primbs, Mathias; Sun, Yanyan; Roy, Aaron
- Energy & Environmental Science, Vol. 13, Issue 8
Electrochemical CO2 Reduction on Metal Electrodes
book, January 2008
- Hori, Y.; Vayenas, Constantinos G.; White, Ralph E.
- Modern Aspects of Electrochemistry, p. 89-189
Ultralight covalent organic framework/graphene aerogels with hierarchical porosity
journal, September 2020
- Li, Changxia; Yang, Jin; Pachfule, Pradip
- Nature Communications, Vol. 11, Issue 1
Wavelet data analysis of EXAFS spectra
journal, June 2009
- Timoshenko, J.; Kuzmin, A.
- Computer Physics Communications, Vol. 180, Issue 6
Diacetylene Functionalized Covalent Organic Framework (COF) for Photocatalytic Hydrogen Generation
journal, January 2018
- Pachfule, Pradip; Acharjya, Amitava; Roeser, Jérôme
- Journal of the American Chemical Society, Vol. 140, Issue 4
Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO 2 Electroreduction to CO and Hydrocarbons
journal, July 2015
- Varela, Ana Sofia; Ranjbar Sahraie, Nastaran; Steinberg, Julian
- Angewandte Chemie, Vol. 127, Issue 37
Elucidating the Electrocatalytic CO 2 Reduction Reaction over a Model Single‐Atom Nickel Catalyst
journal, December 2019
- Liu, Song; Yang, Hong Bin; Hung, Sung‐Fu
- Angewandte Chemie, Vol. 132, Issue 2
Single site porphyrine-like structures advantages over metals for selective electrochemical CO2 reduction
journal, June 2017
- Bagger, Alexander; Ju, Wen; Varela, Ana Sofia
- Catalysis Today, Vol. 288
Covalent triazine framework modified with coordinatively-unsaturated Co or Ni atoms for CO 2 electrochemical reduction
journal, January 2018
- Su, Panpan; Iwase, Kazuyuki; Harada, Takashi
- Chemical Science, Vol. 9, Issue 16
Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution
journal, January 1989
- Hori, Yoshio; Murata, Akira; Takahashi, Ryutaro
- Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 8
Efficient electron transmission in covalent organic framework nanosheets for highly active electrocatalytic carbon dioxide reduction
journal, January 2020
- Zhu, Hong-Jing; Lu, Meng; Wang, Yi-Rong
- Nature Communications, Vol. 11, Issue 1
Coordinatively unsaturated nickel–nitrogen sites towards selective and high-rate CO 2 electroreduction
journal, January 2018
- Yan, Chengcheng; Li, Haobo; Ye, Yifan
- Energy & Environmental Science, Vol. 11, Issue 5
Silica-Templated Covalent Organic Framework-Derived Fe–N-Doped Mesoporous Carbon as Oxygen Reduction Electrocatalyst
journal, April 2019
- Zhao, Xiaojia; Pachfule, Pradip; Li, Shuang
- Chemistry of Materials, Vol. 31, Issue 9
Elucidating the Electrocatalytic CO 2 Reduction Reaction over a Model Single‐Atom Nickel Catalyst
journal, January 2020
- Liu, Song; Yang, Hong Bin; Hung, Sung‐Fu
- Angewandte Chemie International Edition, Vol. 59, Issue 2
New interpretations of XPS spectra of nickel metal and oxides
journal, May 2006
- Grosvenor, Andrew P.; Biesinger, Mark C.; Smart, Roger St. C.
- Surface Science, Vol. 600, Issue 9
Exclusive Ni–N 4 Sites Realize Near-Unity CO Selectivity for Electrochemical CO 2 Reduction
journal, October 2017
- Li, Xiaogang; Bi, Wentuan; Chen, Minglong
- Journal of the American Chemical Society, Vol. 139, Issue 42
Integration of Strong Electron Transporter Tetrathiafulvalene into Metalloporphyrin-Based Covalent Organic Framework for Highly Efficient Electroreduction of CO 2
journal, February 2020
- Wu, Qiao; Xie, Rui-Kuan; Mao, Min-Jie
- ACS Energy Letters, Vol. 5, Issue 3
Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2
journal, October 2017
- Ju, Wen; Bagger, Alexander; Hao, Guang-Ping
- Nature Communications, Vol. 8, Issue 1
Covalent organic frameworks comprising cobalt porphyrins for catalytic CO 2 reduction in water
journal, August 2015
- Lin, Song; Diercks, Christian S.; Zhang, Yue-Biao
- Science, Vol. 349, Issue 6253
Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction
journal, January 2018
- Diercks, Christian S.; Lin, Song; Kornienko, Nikolay
- Journal of the American Chemical Society, Vol. 140, Issue 3
High-performance fuel cell cathodes exclusively containing atomically dispersed iron active sites
journal, January 2019
- Zhang, Hanguang; Chung, Hoon T.; Cullen, David A.
- Energy & Environmental Science, Vol. 12, Issue 8
Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N‐doped Carbon Catalysts
journal, January 2020
- Koshy, David M.; Chen, Shucheng; Lee, Dong Un
- Angewandte Chemie, Vol. 132, Issue 10
Atomically dispersed Ni species on N-doped carbon nanotubes for electroreduction of CO2 with nearly 100% CO selectivity
journal, August 2020
- Hou, Ying; Liang, Yu-Lin; Shi, Peng-Chao
- Applied Catalysis B: Environmental, Vol. 271
Nickel Doping Enhances the Reactivity of Fe 3 O 4 (001) to Water
journal, May 2019
- Jakub, Zdenek; Hulva, Jan; Mirabella, Francesca
- The Journal of Physical Chemistry C, Vol. 123, Issue 24
Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction
journal, August 2020
- Zhang, Xiao; Wang, Yang; Gu, Meng
- Nature Energy, Vol. 5, Issue 9
Surface effects in the Ni x-ray photoemission spectra of NiO
journal, June 2007
- Soriano, L.; Preda, I.; Gutiérrez, A.
- Physical Review B, Vol. 75, Issue 23
Nanostructured electrocatalysts with tunable activity and selectivity
journal, March 2016
- Mistry, Hemma; Varela, Ana Sofia; Kühl, Stefanie
- Nature Reviews Materials, Vol. 1, Issue 4
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation
journal, September 2017
- Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu
- Journal of the American Chemical Society, Vol. 139, Issue 40
Efficient CO 2 to CO electrolysis on solid Ni–N–C catalysts at industrial current densities
journal, January 2019
- Möller, Tim; Ju, Wen; Bagger, Alexander
- Energy & Environmental Science, Vol. 12, Issue 2
Deconvolution of Utilization, Site Density, and Turnover Frequency of Fe–Nitrogen–Carbon Oxygen Reduction Reaction Catalysts Prepared with Secondary N-Precursors
journal, January 2018
- Leonard, Nathaniel D.; Wagner, Stephan; Luo, Fang
- ACS Catalysis, Vol. 8, Issue 3
Surface site density and utilization of platinum group metal (PGM)-free Fe–NC and FeNi–NC electrocatalysts for the oxygen reduction reaction
journal, January 2021
- Luo, Fang; Wagner, Stephan; Onishi, Ichiro
- Chemical Science, Vol. 12, Issue 1
Unified mechanistic understanding of CO2 reduction to CO on transition metal and single atom catalysts
journal, November 2021
- Vijay, Sudarshan; Ju, Wen; Brückner, Sven
- Nature Catalysis, Vol. 4, Issue 12
Transition-Metal Single Atoms in a Graphene Shell as Active Centers for Highly Efficient Artificial Photosynthesis
journal, December 2017
- Jiang, Kun; Siahrostami, Samira; Akey, Austin J.
- Chem, Vol. 3, Issue 6
High and Reversible Lithium Ion Storage in Self-Exfoliated Triazole-Triformyl Phloroglucinol-Based Covalent Organic Nanosheets
journal, November 2017
- Haldar, Sattwick; Roy, Kingshuk; Nandi, Shyamapada
- Advanced Energy Materials, Vol. 8, Issue 8
Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N‐doped Carbon Catalysts
journal, January 2020
- Koshy, David M.; Chen, Shucheng; Lee, Dong Un
- Angewandte Chemie International Edition, Vol. 59, Issue 10
Nitrogen-Stabilized Low-Valent Ni Motifs for Efficient CO 2 Electrocatalysis
journal, December 2019
- Wen, Chun Fang; Mao, Fangxin; Liu, Yuanwei
- ACS Catalysis, Vol. 10, Issue 2
Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction
journal, February 2018
- Yang, Hong Bin; Hung, Sung-Fu; Liu, Song
- Nature Energy, Vol. 3, Issue 2
Atomically Defined Undercoordinated Active Sites for Highly Efficient CO 2 Electroreduction
journal, November 2019
- Zheng, Wanzhen; Yang, Jian; Chen, Hengquan
- Advanced Functional Materials, Vol. 30, Issue 4
Prospects of CO2 Utilization via Direct Heterogeneous Electrochemical Reduction
journal, December 2010
- Whipple, Devin T.; Kenis, Paul J. A.
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 24, p. 3451-3458
Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N 2 and H 2 O
journal, February 2020
- Mukherjee, Shreya; Yang, Xiaoxuan; Shan, Weitao
- Small Methods, Vol. 4, Issue 6
Electrochemical Reduction of CO 2 Catalyzed by Fe-N-C Materials: A Structure–Selectivity Study
journal, January 2017
- Huan, Tran Ngoc; Ranjbar, Nastaran; Rousse, Gwenaëlle
- ACS Catalysis, Vol. 7, Issue 3
Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO 2 Electroreduction to CO and Hydrocarbons
journal, July 2015
- Varela, Ana Sofia; Ranjbar Sahraie, Nastaran; Steinberg, Julian
- Angewandte Chemie International Edition, Vol. 54, Issue 37
Isolated Ni single atoms in graphene nanosheets for high-performance CO 2 reduction
journal, January 2018
- Jiang, Kun; Siahrostami, Samira; Zheng, Tingting
- Energy & Environmental Science, Vol. 11, Issue 4
Unraveling Mechanistic Reaction Pathways of the Electrochemical CO 2 Reduction on Fe–N–C Single-Site Catalysts
journal, June 2019
- Ju, Wen; Bagger, Alexander; Wang, Xingli
- ACS Energy Letters, Vol. 4, Issue 7
Macro/Microporous Covalent Organic Frameworks for Efficient Electrocatalysis
journal, March 2019
- Zhao, Xiaojia; Pachfule, Pradip; Li, Shuang
- Journal of the American Chemical Society, Vol. 141, Issue 16