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Development of solar fuels photoanodes through combinatorial integration of Ni–La–Co–Ce oxide catalysts on BiVO₄

Guevarra, D. and Shinde, A. and Suram, S. K. and Sharp, I. D. and Toma, F. M. and Haber, J. A. and Gregoire, J. M. (2016) Development of solar fuels photoanodes through combinatorial integration of Ni–La–Co–Ce oxide catalysts on BiVO₄. Energy and Environmental Science, 9 (2). pp. 565-580. ISSN 1754-5692. doi:10.1039/c5ee03488d.

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The development of an efficient photoanode remains the primary materials challenge in the establishment of a scalable technology for solar water splitting. The typical photoanode architecture consists of a semiconductor light absorber coated with a metal oxide that serves a combination of functions, including corrosion protection, electrocatalysis, light trapping, hole transport, and elimination of deleterious recombination sites. To date, such coatings have been mostly limited to simple materials such as TiO₂ and Co-Pi, with extensive experimental and theoretical effort required to provide an understanding of the physics and chemistry of the semiconductor-coating interface. To provide a more efficient exploration of metal oxide coatings for a given light absorber, we introduce a high throughput methodology wherein a uniform BiVO₄ thin film is coated with 858 unique metal oxides covering a range of metal oxide loadings and the full Ni–La–Co–Ce oxide quaternary composition space. Photoelectrochemical characterization of each photoanode reveals that approximately one third of the coatings lower the photoanode performance while select combinations of metal oxide composition and loading provide up to a 14-fold increase in the maximum photoelectrochemical power generation for oxygen evolution in pH 13 electrolyte. Particular Ce-rich coatings also exhibit an anti-reflection effect that further amplifies the performance, yielding a 20-fold enhancement in power conversion efficiency compared to bare BiVO₄. By use of in situ optical spectroscopy and comparisons between the metal oxide coatings and their extrinsic optical and electrocatalytic properties, we present a suite of data-driven discoveries, including composition regions which form optimal interfaces with BiVO₄ and photoanodes that are suitable for integration with a photocathode due to their excellent power conversion and solar transmission efficiencies. The high throughput experimentation and informatics provides a powerful platform for both identifying the pertinent interfaces for further study and discovering high performance photoanodes for incorporation into efficient water splitting devices.

Item Type:Article
Related URLs:
URLURL TypeDescription
Guevarra, D.0000-0002-9592-3195
Shinde, A.0000-0003-2386-3848
Suram, S. K.0000-0001-8170-2685
Sharp, I. D.0000-0001-5238-7487
Toma, F. M.0000-0003-2332-0798
Haber, J. A.0000-0001-7847-5506
Gregoire, J. M.0000-0002-2863-5265
Additional Information:© 2015 The Royal Society of Chemistry. Received 17th November 2015, Accepted 9th December 2015, First published online 09 Dec 2015. 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 (Award No. DE-SC0004993). The authors thank Citrine Informatics ( for data hosting. The raw potentiostat and spectrometer data for the anodic sweep of the CV for each photoanode are available at
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Issue or Number:2
Record Number:CaltechAUTHORS:20151221-160606238
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:63116
Deposited By: Tony Diaz
Deposited On:22 Dec 2015 17:33
Last Modified:26 Apr 2022 17:19

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