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Identification of active sites for acidic oxygen reduction on carbon catalysts with and without nitrogen doping

Nature Catalysis volume 2, pages 688–695 (2019)Cite this article

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Abstract

Owing to the difficulty in controlling the dopant or defect types and their homogeneity in carbon materials, it is still a controversial issue to identify the active sites of carbon-based metal-free catalysts. Here we report a proof-of-concept study on the active-site evaluation for a highly oriented pyrolytic graphite catalyst with specific pentagon carbon defective patterns (D-HOPG). It is demonstrated that specific carbon defect types (an edged pentagon in this work) could be selectively created via controllable nitrogen doping. Work-function analyses coupled with macro and micro-electrochemical performance measurements suggest that the pentagon defects in D-HOPG served as major active sites for the acidic oxygen reduction reaction, even much superior to the pyridinic nitrogen sites in nitrogen-doped highly oriented pyrolytic graphite. This work enables us to elucidate the relative importance of the specific carbon defects versus nitrogen-dopant species and their respective contributions to the observed overall acidic oxygen reduction reaction activity.

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Fig. 1: Synthetic scheme and structure characterization of D-HOPG.
Fig. 2: Structure characterization of the formation of specific carbon defects via controllable nitrogen-doping species.
Fig. 3: The intrinsic work function analysis and macro-electrocatalytic effects of a nitrogen dopant and carbon defect in an acidic ORR.
Fig. 4: Identification of the active location in D-HOPG via KPFM and micro-electrocatalytic analysis.
Fig. 5: Unveiling the derived carbon defect as the active site for an enhanced ORR.

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The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

The authors thank the Australia Research Council for financial support (ARC DP170103317, ARC DP170102267 and ARC DP190103881). Y.J. also thanks the ARC for an ARC Discovery Early Career Researcher Award (ARC DE180101030). The authors thank the Australian National Fabrication Facility (ANFF)—Materials Node, the University of Wollongong Electron Microscopy Centre and Canadian Light Source for equipment access.

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Author notes

  1. These authors contributed equally: Y. Jia and L. Z. Zhang.

Authors and Affiliations

  1. School of Environment and Science, Queensland Micro- and Nanotechnology Centre, Griffith University, Nathan Campus, Brisbane, Queensland, Australia

    Yi Jia, Longzhou Zhang, Xuecheng Yan, Xin Wang & Xiangdong Yao

  2. School of Materials Science and Engineering, Yunnan Key Laboratory for Micro/nano Materials & Technology, Yunnan University, Kunming, China

    Longzhou Zhang

  3. School of Chemical Engineering, The University of Queensland, Brisbane, Queensland, Australia

    Linzhou Zhuang & Zhonghua Zhu

  4. Collaborative Innovation Center for Marine Biomass Fibers, Materials and Textiles of Shandong Province, Institute of Marine Biobased Materials, College of Environmental Science and Engineering, Qingdao University, Qingdao, China

    Hongli Liu & Dongjiang Yang

  5. Division of Nanomaterials and Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry, University of Science and Technology of China, Hefei, China

    Xin Wang, Jiandang Liu & Yarong Zheng

  6. Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Ministry of Education and Shanxi Province, Taiyuan, China

    Jiancheng Wang

  7. State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China

    Zhaohui Xiao & Shuangyin Wang

  8. Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Australian National Fabrication Facility—Queensland Node, Brisbane, Queensland, Australia

    Elena Taran

  9. Intelligent Polymer Research Institute, ARC Centre of Excellence for Electromaterials Science, AIIM Facility, University of Wollongong, Innovation Campus, Wollongong, New South Wales, Australia

    Jun Chen

  10. CWRU-UNSW International Joint Laboratory, Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH, USA

    Liming Dai

  11. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, China

    Xiangdong Yao

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  1. Yi Jia
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Contributions

X.Y. and L.D. conceived and designed the project. X.Y. supervised the project. Y.J. and L.Zhang prepared the samples and did the electrocatalytic performances test. L.Zhang, L.Zhuang, X.Y. and Z.Z. performed the characterizations, which included XPS, scanning electron microscopy and Raman spectroscopy. J.W. did the XAS. J.C. performed the transition electron microscopy. X.W., J.L. and Y.Z. performed PA. E.T. did the AFM. Z.X. and S.W. performed the micro-electrocatalytic measurements. H.L. and D.Y. performed the DFT calculations. Y.J., L.Zhang, X.Y. and L.D. wrote the manuscript. Y.J. and L.Zhang contributed equally to this work. All the authors discussed the results and commented on the manuscript.

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Correspondence to Liming Dai or Xiangdong Yao.

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Jia, Y., Zhang, L., Zhuang, L. et al. Identification of active sites for acidic oxygen reduction on carbon catalysts with and without nitrogen doping. Nat Catal 2, 688–695 (2019). https://doi.org/10.1038/s41929-019-0297-4

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