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Understanding the Dynamics of Molecular Water Oxidation Catalysts with Liquid-Phase Transmission Electron Microscopy: The Case of Vitamin B12

  • Zahra Abdi
    Zahra Abdi
    Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731, Iran
    More by Zahra Abdi
  • S. Esmael Balaghi
    S. Esmael Balaghi
    Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich, Switzerland
  • Alla S. Sologubenko
    Alla S. Sologubenko
    Scientific Center of Optical and Electron Microscopy (ScopeM), ETH Zurich, Otto-Stern-Weg 3, CH-8093 Zurich, Switzerland
  • Marc-Georg Willinger
    Marc-Georg Willinger
    Scientific Center of Optical and Electron Microscopy (ScopeM), ETH Zurich, Otto-Stern-Weg 3, CH-8093 Zurich, Switzerland
  • Matthias Vandichel
    Matthias Vandichel
    Department of Chemical Sciences and Bernal Institute, Limerick University, V94 T9PX Limerick, Ireland
  • Jian-Ren Shen
    Jian-Ren Shen
    Research Institute for Interdisciplinary Science and Graduate School of Natural Science and Technology, Okayama University, Okayama 700-8530, Japan
  • Suleyman I. Allakhverdiev*
    Suleyman I. Allakhverdiev
    K. A. Timiryazev Institute of Plant Physiology, Russian Academy of Sciences, Botanicheskaya Street 35, Moscow 127276, Russia
    *Email: [email protected]
  • Greta R. Patzke*
    Greta R. Patzke
    Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich, Switzerland
    *Email: [email protected]
  • , and 
  • Mohammad Mahdi Najafpour*
    Mohammad Mahdi Najafpour
    Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731, Iran
    Center of Climate Change and Global Warming, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731, Iran
    Research Center for Basic Sciences & Modern Technologies (RBST), Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731, Iran
    *Email: [email protected]
Cite this: ACS Sustainable Chem. Eng. 2021, 9, 28, 9494–9505
Publication Date (Web):July 7, 2021
https://doi.org/10.1021/acssuschemeng.1c03539
Copyright © 2021 American Chemical Society
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Supporting Info (2)»

Abstract

Cobalt compounds are intensely explored as efficient catalysts for the oxygen evolution reaction (OER). Since vitamin B12 is a soluble cobalt compound with high enzymatic activity, evaluating its OER activity is of relevance for biomimetic catalyst research. In this work, the temporal evolution of a homogenous vitamin B12 catalyst in the early stages of OER was investigated by an advanced combination of in situ electrochemical liquid transmission electron microscopy (EC-LTEM), in situ UV–vis spectroelectrochemistry, and extended X-ray absorption fine structure (EXAFS) methods. For the first time, we provided direct evidence of diffuse layer dynamics on the working electrode interface. The results suggested that the formation of cobalt oxyphosphate nanoparticles on the working electrode interface and in the presence of phosphate buffer is the initial stage of the catalytic pathway. Computational results confirmed that the ligand oxidation pathway could occur at potentials below the OER thermodynamic barrier (1.23 V vs reversible hydrogen electrode (RHE)), which leads to a Co ion leaching into the electrolyte. This study showed that investigation of the apparent molecular mechanisms of OER with metal complexes requires careful analyses. We illustrate the high precision and sensitivity of EC-LTEM under operational conditions to monitor heterogeneous catalysts generated during OER and to evaluate their actual roles in the catalytic process.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.1c03539.

  • Details of the in situ electrochemical liquid TEM setup, the in situ visible spectroelectrochemistry setup, PXRD data, SEM–EDX characterizations, XP spectra, complementary EIS and voltammetry data, additional computational data, and XAS fitting data (PDF)

  • In situ EC-LTEM image sequences (AVI)

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