Solar fuel photoanodes prepared by inkjet printing of copper vanadates
Abstract
Widespread deployment of solar fuel generators requires the development of efficient and scalable functional materials, especially for photoelectrocatalysis of the oxygen evolution reaction. Metal oxides comprise the most promising class of photoanode materials, but no known material meets the demanding photoelectrochemical requirements. Copper vanadates have recently been identified as a promising class of photoanode materials with several phases exhibiting an indirect band gap near 2 eV and stable photoelectrocatalysis of the oxygen evolution reaction in a pH 9.2 electrolyte. By employing combinatorial inkjet printing of metal precursors and applying both calcination and rapid thermal processing, we characterize the phase behaviour of the entire CuO–V_2O_5 composition space for different thermal treatments via automated analysis of approximately 100 000 Raman spectra acquired using a novel Raman imaging technique. These results enable the establishment of structure–property relationships for optical absorption and photoelectrochemical properties, revealing that highly active photoelectrocatalysts containing α-Cu_2V_2O_7 or α-CuV_2O_6 can be prepared using scalable solution processing techniques. An additional discovery results from the formation of an off-stoichiometric β-Cu_2V_2O_7 material that exhibits high photoelectroactivity in the presence of a ferri/ferrocyanide redox couple with excellent stability in a pH 13 electrolyte, demonstrating that copper vanadates may be viable photoanodes in strong alkaline electrolytes.
Additional Information
© 2016 The Royal Society of Chemistry. Received 10 Feb 2016, Accepted 11 Apr 2016. First published online 11 Apr 2016. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. The authors thank Natalie Becerra-Stasiewicz for assistance with acquisition of the SEM images, Santosh Suram for assistance with UV-vis data, Joel Haber for helpful discussion and Florian Brown-Altvater for assistance with the Raman calculations.Attached Files
Published - c6ta01252c.pdf
Supplemental Material - c6ta01252c1.pdf
Supplemental Material - c6ta01252c2.zip
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Additional details
- Eprint ID
- 66581
- Resolver ID
- CaltechAUTHORS:20160502-100311001
- Department of Energy (DOE)
- DE-SC0004993
- Created
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2016-05-02Created from EPrint's datestamp field
- Updated
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2021-11-11Created from EPrint's last_modified field
- Caltech groups
- JCAP