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In-situ ECSTM investigation of H2O2 production in cobalt—porphyrin-catalyzed oxygen reduction reaction

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Abstract

We report the in-situ investigation of the production of H2O2 in 5,10,15,20-tetra(4-methoxyphenyl)-21H,23H-porphyrin cobalt(II) (CoTMPP)-catalyzed oxygen reduction reaction (ORR) in neutral electrolytes by electrochemical scanning tunneling microscopy (ECSTM) at the molecular scale. The adsorption of OOH− on active sites can be observed in STM images and is found to be correlated with the pH value of the electrolyte. The thermodynamic parameters of the formation of CoTMPP—OOH− complex are extracted by the quantitative analysis of the STM images. Two stages of the ORR including the formation of H2O2 and further reduction of H2O2 at different reduction potentials can be revealed by electrochemical measurements. In-situ ECSTM experiments unambiguously identify the formation of the CoTMPP—OOH− complex as the high contrast species and its reduction and oxidation process. This work provides the direct evidence for understanding the formation and transformation process of H2O2 at the molecular scale, which benefits the rational design of the high-efficiency electrocatalysts for ORR and H2O2 production.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2021YFA1501002), the National Natural Science Foundation of China (21725306 and 21972147), the Key Research Program of the Chinese Academy of Sciences (XDPB01), and the National Postdoctoral Program for Innovative Talents (BX20220307) of the Chinese Postdoctoral Science Foundation. The Supercomputing Environment of the Chinese Academy of Sciences is acknowledged for providing computational resources.

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Authors and Affiliations

  1. CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, CAS Research/Education Center for Excellence in Molecular Sciences, Beijing National Laboratory for Molecular Science (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Ya-Chen Feng, Xiang Wang, Zhen-Yu Yi, Yu-Qi Wang, Hui-Juan Yan & Dong Wang

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Ya-Chen Feng, Zhen-Yu Yi, Yu-Qi Wang, Hui-Juan Yan & Dong Wang

Authors
  1. Ya-Chen Feng
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  2. Xiang Wang
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  3. Zhen-Yu Yi
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  4. Yu-Qi Wang
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  5. Hui-Juan Yan
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  6. Dong Wang
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Correspondence to Dong Wang.

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The authors declare no conflict of interest.

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The supporting information is available online at chem.scichina.com and link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Feng, YC., Wang, X., Yi, ZY. et al. In-situ ECSTM investigation of H2O2 production in cobalt—porphyrin-catalyzed oxygen reduction reaction. Sci. China Chem. 66, 273–278 (2023). https://doi.org/10.1007/s11426-022-1465-8

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  • DOI: https://doi.org/10.1007/s11426-022-1465-8

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