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Issue 2, 2015
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Mechanistic insights into solar water oxidation by cobalt-phosphate-modified α-Fe2O3 photoanodes

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Abstract

Interfacing α-Fe2O3 photoanodes with the water-oxidation electrocatalyst Co-Pi is known to enhance their photon-to-current conversion efficiencies by reducing electron–hole recombination near their surfaces, particularly at more negative potentials, but the mechanism by which Co-Pi modification achieves this enhancement remains poorly understood. Conflicting experimental observations have been recorded with respect to the role of Co-Pi thickness and even the participation of Co-Pi in catalysis, raising important general questions concerning the fundamental properties of catalyst-modified PEC water-oxidation photoanodes for solar energy conversion. Here, we report results from electrochemical, spectroscopic, and microscopic measurements on mesostructured Co-Pi/α-Fe2O3 composite photoanodes that reveal evolving pathways of water oxidation with increasing Co-Pi thickness. These results highlight major fundamental differences between structured and planar Co-Pi/α-Fe2O3 composite photoanodes and help to reconcile previously conflicting mechanistic interpretations.

Graphical abstract: Mechanistic insights into solar water oxidation by cobalt-phosphate-modified α-Fe2O3 photoanodes

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Publication details

The article was received on 09 Sep 2014, accepted on 20 Nov 2014 and first published on 21 Nov 2014


Article type: Paper
DOI: 10.1039/C4EE02869D
Author version available: Download Author version (PDF)
Citation: Energy Environ. Sci., 2015,8, 577-584
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    Mechanistic insights into solar water oxidation by cobalt-phosphate-modified α-Fe2O3 photoanodes

    G. M. Carroll, D. K. Zhong and D. R. Gamelin, Energy Environ. Sci., 2015, 8, 577
    DOI: 10.1039/C4EE02869D

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