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Incorporation of Multinuclear Copper Active Sites into Nitrogen-Doped Graphene for Electrochemical Oxygen Reduction

  • Masaru Kato*
    Masaru Kato
    Faculty of Environmental Earth Science  and  Graduate School of Environmental Science, Hokkaido University, N10W5, Kita-ku, Sapporo 060-0810, Japan
    Global Research Center for Environment and Energy based on Nanomaterials Science (GREEN), National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan
    *E-mail: [email protected] (M.K.).
    More by Masaru Kato
  • Marika Muto
    Marika Muto
    Graduate School of Environmental Science, Hokkaido University, N10W5, Kita-ku, Sapporo 060-0810, Japan
    Global Research Center for Environment and Energy based on Nanomaterials Science (GREEN), National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan
    More by Marika Muto
  • Naohiro Matsubara
    Naohiro Matsubara
    Graduate School of Environmental Science, Hokkaido University, N10W5, Kita-ku, Sapporo 060-0810, Japan
    Global Research Center for Environment and Energy based on Nanomaterials Science (GREEN), National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan
  • Yohei Uemura
    Yohei Uemura
    Department of Materials Molecular Science, Institute for Molecular Science, Myodaiji-cho, Okazaki 444-8585, Japan
    More by Yohei Uemura
  • Yuki Wakisaka
    Yuki Wakisaka
    Institute for Catalysis, Hokkaido University, N21W10, Kita-ku, Sapporo 001-0021, Japan
  • Tsubasa Yoneuchi
    Tsubasa Yoneuchi
    Graduate School of Environmental Science, Hokkaido University, N10W5, Kita-ku, Sapporo 060-0810, Japan
    Global Research Center for Environment and Energy based on Nanomaterials Science (GREEN), National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan
  • Daiju Matsumura
    Daiju Matsumura
    Materials Sciences Research Center, Japan Atomic Energy Agency, 1-1-1 Koto, Sayo, Hyogo 679-5165, Japan
  • Tomoko Ishihara
    Tomoko Ishihara
    Soft X-ray Spectroscopy Instrumentation Unit, RIKEN Spring-8 Center, RIKEN, Sayo-cho, Sayo, Hyogo 679-5148, Japan
  • Takashi Tokushima
    Takashi Tokushima
    Soft X-ray Spectroscopy Instrumentation Unit, RIKEN Spring-8 Center, RIKEN, Sayo-cho, Sayo, Hyogo 679-5148, Japan
  • Shin-ichiro Noro
    Shin-ichiro Noro
    Faculty of Environmental Earth Science  and  Graduate School of Environmental Science, Hokkaido University, N10W5, Kita-ku, Sapporo 060-0810, Japan
  • Satoru Takakusagi
    Satoru Takakusagi
    Institute for Catalysis, Hokkaido University, N21W10, Kita-ku, Sapporo 001-0021, Japan
  • Kiyotaka Asakura
    Kiyotaka Asakura
    Institute for Catalysis, Hokkaido University, N21W10, Kita-ku, Sapporo 001-0021, Japan
  • , and 
  • Ichizo Yagi*
    Ichizo Yagi
    Faculty of Environmental Earth Science  and  Graduate School of Environmental Science, Hokkaido University, N10W5, Kita-ku, Sapporo 060-0810, Japan
    Global Research Center for Environment and Energy based on Nanomaterials Science (GREEN), National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan
    *E-mail: [email protected] (I.Y.).
    More by Ichizo Yagi
Cite this: ACS Appl. Energy Mater. 2018, 1, 5, 2358–2364
Publication Date (Web):April 9, 2018
https://doi.org/10.1021/acsaem.8b00491
Copyright © 2018 American Chemical Society

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    Abstract

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    Multinuclear metal active sites are widely used as catalytic reaction centers in metalloenzymes and generally show high catalytic activity. For example, laccases are known to catalyze the oxygen reduction reaction (ORR) to water at a multinuclear copper site with almost no energy loss. The ORR is an important reaction not only in oxygenic respiration but also in future energy generation devices such as polymer electrolyte fuel cells and metal–air batteries. For large-scale commercialization of these devices, there is a need to develop highly active ORR electrocatalysts based on nonprecious metals. Incorporation of multinuclear metal active sites in conductive materials such as carbon will allow us to develop highly active electrocatalysts like metalloenzymes. However, such methods had not been established yet. Herein, we report a copper-based ORR electrocatalyst with multinuclear copper active sites in nitrogen-doped graphene. The electrocatalyst was synthesized from the mixture of graphene oxide and a multinuclear copper complex in a short-period heating method. Electrochemical measurements revealed that the obtained electrocatalyst showed the highest electrocatalytic activity for the ORR in the Cu-based electrocatalysts in neutral aqueous solution. Physicochemical measurements including in situ X-ray absorption spectroscopy revealed the incorporation of multinuclear copper sites. Our synthetic approach will offer guidance for developing highly active electrocatalysts utilizing multinuclear metal sites not only for the ORR but also for other electrocatalytic reactions.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsaem.8b00491.

    • Experimental section, XRD patterns, cyclic voltammograms, linear sweep voltammograms, TEM images, an N2 adsorption/desorption isotherm, X-ray photoelectron spectra, Raman spectra, XANES data, EXAFS data and a list of abbreviations of the samples used (PDF)

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    Cited By

    This article is cited by 16 publications.

    1. Bandhana Devi, Akhil Bhardwaj, Diksha Gambhir, Biswajit Roy, Anirban Karmakar, Gourab Dey, Anuj Jain, Bhaskar Mondal, Rik Rani Koner. Cu(II)-Based Coordination Polymer as a Pristine Form Usable Electrocatalyst for Oxygen Reduction Reaction: Experimental Evaluation and Theoretical Insights into Biomimetic Mechanistic Aspects. Inorganic Chemistry 2022, 61 (39) , 15699-15710. https://doi.org/10.1021/acs.inorgchem.2c02755
    2. Deborah Brazzolotto, Yannig Nédellec, Christian Philouze, Michael Holzinger, Fabrice Thomas, Alan Le Goff. Functionalizing Carbon Nanotubes with Bis(2,9-dialkyl-1,10-phenanthroline)copper(II) Complexes for the Oxygen Reduction Reaction. Inorganic Chemistry 2022, 61 (38) , 14997-15006. https://doi.org/10.1021/acs.inorgchem.2c01791
    3. Jinxiu Han, Ni Wang, Xialiang Li, Wei Zhang, Rui Cao. Improving Electrocatalytic Oxygen Reduction Activity and Selectivity with a Cobalt Corrole Appended with Multiple Positively Charged Proton Relay Sites. The Journal of Physical Chemistry C 2021, 125 (45) , 24805-24813. https://doi.org/10.1021/acs.jpcc.1c07578
    4. Masaru Kato, Natsuki Fujibayashi, Daiki Abe, Naohiro Matsubara, Satoshi Yasuda, Ichizo Yagi. Impact of Heterometallic Cooperativity of Iron and Copper Active Sites on Electrocatalytic Oxygen Reduction Kinetics. ACS Catalysis 2021, 11 (4) , 2356-2365. https://doi.org/10.1021/acscatal.0c04753
    5. Hui Zhang, Yichuan Li, Lingyou Zeng, Yuan Pan. Atomic‐Level Regulation of Cu‐Based Electrocatalyst for Enhancing Oxygen Reduction Reaction: From Single Atoms to Polymetallic Active Sites. Small 2024, 20 (8) https://doi.org/10.1002/smll.202307384
    6. Masaru Kato, Ichizo Yagi. Bio-inspired Cu, Fe-codoped carbon electrocatalysts for the oxygen reduction reaction. 2024, 289-298. https://doi.org/10.1016/B978-0-323-85669-0.00047-7
    7. Tianmi Tang, Xue Bai, Zhenlu Wang, Jingqi Guan. Structural engineering of atomic catalysts for electrocatalysis. Chemical Science 2024, 2 https://doi.org/10.1039/D4SC00569D
    8. Xiao Zhang, Gui-Shan Chen, Hao-Cheng Liu, Ming-Jun Zhu, Ming-Yi Xie, Ming-Sheng Cen, Qi-Jun Li, Tian-Shun Wang, Hua-Xin Zhang. Bidirectional O2 reduction/H2O oxidation boosted by a pentadentate pyridylalkylamine copper(II) complex. Electrochimica Acta 2023, 446 , 142099. https://doi.org/10.1016/j.electacta.2023.142099
    9. Yimei Gao, Haitao Lei, Zijia Bao, Xinrong Liu, Lingshuang Qin, Zhiyuan Yin, Huiyuan Li, Shu Huang, Wei Zhang, Rui Cao. Electrocatalytic oxygen reduction with cobalt corroles bearing cationic substituents. Physical Chemistry Chemical Physics 2023, 25 (6) , 4604-4610. https://doi.org/10.1039/D2CP05786G
    10. Yimei Gao, Haitao Lei, Hongbo Guo, Jia Meng, Qingxin Zhang, Qian Zhao, Jingwen Li, Zhou Zhou, Weiguo Feng, Wei Zhang, Rui Cao. A cobalt corrole with a biologically relevant imidazolium pendant for boosted electrocatalytic oxygen reduction. Journal of Porphyrins and Phthalocyanines 2023, 27 (01n04) , 719-727. https://doi.org/10.1142/S1088424623500748
    11. Karina Muñoz-Becerra, José H. Zagal, Ricardo Venegas, Francisco J. Recio. Strategies to improve the catalytic activity and stability of bioinspired Cu molecular catalysts for the ORR. Current Opinion in Electrochemistry 2022, 35 , 101035. https://doi.org/10.1016/j.coelec.2022.101035
    12. Masaru KATO, Ichizo YAGI. In situ X-ray Absorption Spectroscopy at Platinum Group Metal (PGM) and Non-PGM Electrocatalysts. Denki Kagaku 2022, 90 (1) , 16-20. https://doi.org/10.5796/denkikagaku.22-FE0005
    13. Xiao Zhang, Ming-Jun Zhu, Gui-Shan Chen, Hao-Cheng Liu, Ming-Yi Xie, Ming-Sheng Chen, Qi-Jun Li, Tian-Shun Wang, Huaxin Zhang. Bidirectional O2 Reduction/H2o Oxidation Boosted by a Pentadentate Pyridylalkylamine Copper(Ii) Complex. SSRN Electronic Journal 2022, 184 https://doi.org/10.2139/ssrn.4175197
    14. Cheng Wang, Jing Li, Zheng Zhou, Yuqi Pan, Zixun Yu, Zengxia Pei, Shenlong Zhao, Li Wei, Yuan Chen. Rechargeable zinc-air batteries with neutral electrolytes: Recent advances, challenges, and prospects. EnergyChem 2021, 3 (4) , 100055. https://doi.org/10.1016/j.enchem.2021.100055
    15. Masaru Kato, Ichizo Yagi. Electrocatalytic Oxygen Reduction at Multinuclear Metal Active Sites Inspired by Metalloenzymes. e-Journal of Surface Science and Nanotechnology 2020, 18 (0) , 81-93. https://doi.org/10.1380/ejssnt.2020.81
    16. Yuewen Yang, Cong Yin, Kai Li, Hao Tang, Ying Wang, Zhijian Wu. Cu Doped Crystalline Carbon-Conjugated g-C 3 N 4 , a Promising Oxygen Reduction Catalyst by Theoretical Study. Journal of The Electrochemical Society 2019, 166 (12) , F755-F759. https://doi.org/10.1149/2.0731912jes

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