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The dataset used here can be found in the respective references or can be shared upon request.
References
Bard, A. J. & Faulkner, L. R. Electrochemical Methods: Fundamentals and Applications (John Wiley & Sons, Inc., 2001).
Zhang, S. & Leng, W. Questioning the rate law in the analysis of water oxidation catalysis on haematite photoanodes. Nat. Chem. https://doi.org/10.1038/s41557-020-00569-y (2020).
Mesa, C. A. et al. Multihole water oxidation catalysis on haematite photoanodes revealed by operando spectroelectrochemistry and DFT. Nat. Chem. 12, 82–89 (2020).
Rosenbluth, M. L. & Lewis, N. S. Ideal behavior of the open circuit voltage of semiconductor/liquid junctions. J. Phys. Chem. 93, 3735–3740 (1989).
Walter, M. G. et al. Solar water splitting cells. Chem. Rev. 110, 6446–6473 (2010).
Lewis, N. S. Progress in understanding electron-transfer reactions at semiconductor/liquid interfaces. J. Phys. Chem. B 102, 4843–4855 (1998).
Kay, A., Cesar, I. & Grätzel, M. New benchmark for water photooxidation by nanostructured α-Fe2O3 films. J. Am. Chem. Soc. 128, 15714–15721 (2006).
Jang, J.-W. et al. Enabling unassisted solar water splitting by iron oxide and silicon. Nat. Commun. 6, 7447 (2015).
Mesa, C. A. et al. Kinetics of photoelectrochemical oxidation of methanol on hematite photoanodes. J. Am. Chem. Soc. 139, 11537–11543 (2017).
Mesa, C. A. et al. Impact of synthesis route on the water oxidation kinetics of hematite photoanodes. J. Phys. Chem. Lett. 11, 7285–7290 (2020).
Le Formal, F. et al. Rate law analysis of water oxidation on a hematite surface. J. Am. Chem. Soc. 137, 6629–6637 (2015).
Upul Wijayantha, K. G., Saremi-Yarahmadi, S. & Peter, L. M. Kinetics of oxygen evolution at α-Fe2O3 photoanodes: a study by photoelectrochemical impedance spectroscopy. Phys. Chem. Chem. Phys. 13, 5264–5270 (2011).
Leng, W. H., Zhang, Z., Zhang, J. Q. & Cao, C. N. Investigation of the kinetics of a TiO2 photoelectrocatalytic reaction involving charge transfer and recombination through surface states by electrochemical impedance spectroscopy. J. Phys. Chem. B 109, 15008–15023 (2005).
Natarajan, A., Oskam, G. & Searson, P. C. The potential distribution at the semiconductor/solution interface. J. Phys. Chem. B 102, 7793–7799 (1998).
Peter, L. Energetics and kinetics of light-driven oxygen evolution at semiconductor electrodes: the example of hematite. J. Solid State Electrochem. 17, 315–326 (2013).
Uosaki, K. & Kita, H. Effects of the Helmholtz layer capacitance on the potential distribution at semiconductor/electrolyte interface and the linearity of the Mott–Schottky plot. J. Electrochem. Soc. 130, 895–897 (1983).
Zhang, Z., Nagashima, H. & Tachikawa, T. Ultra-narrow depletion layers in hematite mesocrystal-based photoanode for boosting multihole water oxidation. Angew. Chem. Int. Ed. 59, 9047–9054 (2020).
Shavorskiy, A. et al. Direct mapping of band positions in doped and undoped hematite during photoelectrochemical water splitting. J. Phys. Chem. Lett. 8, 5579–5586 (2017).
Barroso, M. et al. Dynamics of photogenerated holes in surface modified α-Fe2O3 photoanodes for solar water splitting. Proc. Natl Acad. Sci. USA 109, 15640–15645 (2012).
Barroso, M., Pendlebury, S. R., Cowan, A. J. & Durrant, J. R. Charge carrier trapping, recombination and transfer in hematite (α-Fe2O3) water splitting photoanodes. Chem. Sci. 4, 2724–2734 (2013).
Le Formal, F. et al. Back electron–hole recombination in hematite photoanodes for water splitting. J. Am. Chem. Soc. 136, 2564–2574 (2014).
Acknowledgements
J.R.D. acknowledges financial support from the European Research Council (project Intersolar 291482). C.A.M. thanks COLCIENCIAS (now Ministry of Science, Technology and Innovation, call 568) for funding. J.R.D., C.A.M., R.R. and S.C. acknowledge H2020 project A-LEAF (732840) and L.F. thanks the European Union for a Marie Curie fellowship (658270). We also thank S. Zhang and W. Leng for their interest in our research and for encouraging insightful scientific debate.
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C.A.M., L.F. and J.R.D. conceived and designed the experiments. C.A.M. performed the data collection, treatment and analysis. C.A.M., R.R. and J.R.D. co-wrote the manuscript. All the authors discussed the results, commented on and revised the manuscript.
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Mesa, C.A., Rao, R.R., Francàs, L. et al. Reply to: Questioning the rate law in the analysis of water oxidation catalysis on haematite photoanodes. Nat. Chem. 12, 1099–1101 (2020). https://doi.org/10.1038/s41557-020-00570-5
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DOI: https://doi.org/10.1038/s41557-020-00570-5
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