Abstract
A leading approach for large-scale electrochemical energy production with minimal global-warming gas emission is to use a renewable source of electricity, such as solar energy, to oxidize water, providing the abundant source of electrons needed in fuel synthesis. We report corrosion-resistant, nanocomposite anodes for the oxidation of water required to produce renewable fuels. Silicon, an earth-abundant element and an efficient photovoltaic material, is protected by atomic layer deposition (ALD) of a highly uniform, 2 nm thick layer of titanium dioxide (TiO2) and then coated with an optically transmitting layer of a known catalyst (3 nm iridium). Photoelectrochemical water oxidation was observed to occur below the reversible potential whereas dark electrochemical water oxidation was found to have low-to-moderate overpotentials at all pH values, resulting in an inferred photovoltage of ~550 mV. Water oxidation is sustained at these anodes for many hours in harsh pH and oxidative environments whereas comparable silicon anodes without the TiO2 coating quickly fail. The desirable electrochemical efficiency and corrosion resistance of these anodes is made possible by the low electron-tunnelling resistance (<0.006 Ω cm2 for p+-Si) and uniform thickness of atomic-layer deposited TiO2.
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Acknowledgements
We thank J-Y. Lee, R. Dinyari and P. Peumans for providing access to the solar simulation setup. We also thank T. Jaramillo, S-J. Choi, K. Kuhl and B. Pinaud for impedence spectroscopy and real hydrogen electrode measurements, as well as their helpful discussions. We thank B. Shin and M. Shandalov for their help in TiO2 deposition and characterization. This work was partially supported by the Stanford Global Climate and Energy Project. We acknowledge support from the Center for Integrated Systems and Precourt Institute for Energy seed grants. Y.W.C. acknowledges financial support from a Stanford Graduate Fellowship.
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Y.W.C. and Y.P. prepared the samples and performed solid state tunnelling measurements. Y.W.C., J.D.P. and S.D. performed the electrochemical measurements. M.G. performed the TEM measurement. Y.W.C. and J.D.P performed the XPS measurements. Y.W.C., J.D.P, C.E.D.C. and P.C.M. designed the experiments and prepared the manuscript.
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Chen, Y., Prange, J., Dühnen, S. et al. Atomic layer-deposited tunnel oxide stabilizes silicon photoanodes for water oxidation. Nature Mater 10, 539–544 (2011). https://doi.org/10.1038/nmat3047
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DOI: https://doi.org/10.1038/nmat3047
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