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Factors affecting bismuth vanadate photoelectrochemical performance

Sinclair, Timothy S. and Hunter, Bryan M. and Winkler, Jay R. and Gray, Harry B. and Müller, Astrid M. (2015) Factors affecting bismuth vanadate photoelectrochemical performance. Materials Horizons, 2 (3). pp. 330-337. ISSN 2051-6347. doi:10.1039/c4mh00156g.

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Bismuth vanadate is a promising photoanode material, but recent reports on undoped BiVO_4 without sublayers and co-catalysts showed large variations in photocurrent generation. We addressed this issue by correlating photoelectrochemical performance with physical properties. We devised a novel anodic electrodeposition procedure with iodide added to the aqueous plating bath, which allowed us to prepare BiVO_4 photoanodes with virtually identical thicknesses but different morphologies, and we could control surface Bi content. Morphologies were quantified from SEM images as distributions of crystallite areas and aspect-ratio-normalised diameters, and their statistical moments were derived. We could obtain clear photocurrent generation trends only from bivariate data analysis. Our experimental evidence suggests that a combination of low Bi/V ratio, small aspect-ratio-normalised diameters, and crystallites sizes that were small enough to provide efficient charge separation yet sufficiently large to prevent mass transport limitations led to highest photoelectrochemical performance.

Item Type:Article
Related URLs:
URLURL TypeDescription
Hunter, Bryan M.0000-0001-8559-9304
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Müller, Astrid M.0000-0002-2785-6808
Additional Information:© 2015 The Royal Society of Chemistry. Received 22 Aug 2014, Accepted 02 Dec 2014, First published online 02 Dec 2014. We thank June Wicks for help with SEM imaging, Matthew Shaner for providing electrodeposited BiVO_4 samples on FTO-glass prepared according to Choi, Richard P. Gerhart for fabrication of the photoelectrochemical cell, and Robert H. Coridan for valuable discussions. Research was performed at the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology. T.S.S. acknowledges a SURF Fellowship in honour of Dr Terry Cole, and B.M.H. is an NSF Graduate Fellow. This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124) and the Arnold and Mabel Beckman Foundation.
Group:CCI Solar Fuels
Funding AgencyGrant Number
Arnold and Mabel Beckman FoundationUNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
Issue or Number:3
Record Number:CaltechAUTHORS:20141222-075342492
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53059
Deposited By: Tony Diaz
Deposited On:22 Dec 2014 18:45
Last Modified:10 Nov 2021 19:47

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