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Mesa CA, Francàs L, Yang KR, et al. Multihole water oxidation catalysis on haematite photoanodes revealed by operando spectroelectrochemistry and DFT. Nat Chem. 2019;12(1):82-89doi: 10.1038/s41557-019-0347-1.
Mesa, C. A., Francàs, L., Yang, K. R., Garrido-Barros, P., Pastor, E., Ma, Y., Kafizas, A., Rosser, T. E., Mayer, M. T., Reisner, E., Grätzel, M., Batista, V. S., & Durrant, J. R. (2020). Multihole water oxidation catalysis on haematite photoanodes revealed by operando spectroelectrochemistry and DFT. Nature chemistry, 12(1), 82-89. https://doi.org/10.1038/s41557-019-0347-1
Mesa, Camilo A, et al. "Multihole water oxidation catalysis on haematite photoanodes revealed by operando spectroelectrochemistry and DFT." Nature chemistry vol. 12,1 (2020): 82-89. doi: https://doi.org/10.1038/s41557-019-0347-1
Mesa CA, Francàs L, Yang KR, Garrido-Barros P, Pastor E, Ma Y, Kafizas A, Rosser TE, Mayer MT, Reisner E, Grätzel M, Batista VS, Durrant JR. Multihole water oxidation catalysis on haematite photoanodes revealed by operando spectroelectrochemistry and DFT. Nat Chem. 2020 Jan;12(1):82-89. doi: 10.1038/s41557-019-0347-1. Epub 2019 Oct 21. PMID: 31636394.
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Nat Chem. 2020 Jan;12(1):82-89. doi: 10.1038/s41557-019-0347-1. Epub 2019 Oct 21.

Multihole water oxidation catalysis on haematite photoanodes revealed by operando spectroelectrochemistry and DFT.

Nature chemistry

Camilo A Mesa, Laia Francàs, Ke R Yang, Pablo Garrido-Barros, Ernest Pastor, Yimeng Ma, Andreas Kafizas, Timothy E Rosser, Matthew T Mayer, Erwin Reisner, Michael Grätzel, Victor S Batista, James R Durrant

Affiliations

  1. Molecular Sciences Research Hub and Centre for Plastic Electronics, Imperial College London, London, UK.
  2. Department of Chemistry and Energy Sciences Institute, Yale University, New Haven, CT, USA.
  3. Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain.
  4. The Grantham Institute, Imperial College London, London, UK.
  5. Christian Doppler Laboratory for Sustainable SynGas Chemistry, Department of Chemistry, University of Cambridge, Cambridge, UK.
  6. Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland.
  7. Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Berlin, Germany.
  8. Department of Chemistry and Energy Sciences Institute, Yale University, New Haven, CT, USA. [email protected].
  9. Molecular Sciences Research Hub and Centre for Plastic Electronics, Imperial College London, London, UK. [email protected].

PMID: 31636394 DOI: 10.1038/s41557-019-0347-1

Abstract

Water oxidation is the key kinetic bottleneck of photoelectrochemical devices for fuel synthesis. Despite advances in the identification of intermediates, elucidating the catalytic mechanism of this multi-redox reaction on metal-oxide photoanodes remains a significant experimental and theoretical challenge. Here, we report an experimental analysis of water oxidation kinetics on four widely studied metal oxides, focusing particularly on haematite. We observe that haematite is able to access a reaction mechanism that is third order in surface-hole density, which is assigned to equilibration between three surface holes and M(OH)-O-M(OH) sites. This reaction exhibits low activation energy (E

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