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The impact of surface composition on the interfacial energetics and photoelectrochemical properties of BiVO4

Nature Energy volume 6, pages 287–294 (2021)Cite this article

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Abstract

The ability to engineer a photoelectrode surface is pivotal for optimizing the properties of any photoelectrode used for solar fuel production. Altering crystal facets exposed on the surface of photoelectrodes has been a major strategy to modify their surface structure. However, there exist numerous ways to terminate the surface even for the same facet, which can considerably alter the photoelectrode properties. Here we report tightly integrated experimental and computational investigations of epitaxial BiVO4 photoelectrodes with vanadium- and bismuth-rich (010) facets. Our study demonstrates that even for the same facet the surface Bi:V ratio has a remarkable impact on the interfacial energetics and photoelectrochemical properties. We also elucidate the microscopic origins of how the surface composition can affect the photoelectrochemical properties. This study opens an unexplored path for understanding and engineering surface energetics via tuning the surface termination/composition of multinary oxide photoelectrodes.

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Fig. 1: Characterization of epitaxial BiVO4 (010) electrodes.
Fig. 2: Experimental and simulated STM images of BiVO4 (010).
Fig. 3: Band alignments of BiVO4 (010).
Fig. 4: Calculated macroscopic Ṽ of BiVO4 (010).
Fig. 5: Photoelectrochemical properties of epitaxial BiVO4 (010) electrodes.

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Data availability

The dataset generated and analysed in the current study are openly available on Qresp44 (Qresp.org) through the University of Chicago node; https://doi.org/10.6084/m9.figshare.13496997.

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Acknowledgements

This work was supported by the National Science Foundation (NSF) under grant no. CHE-1764399. This research used resources of the Center for Functional Nanomaterials, which is a US DOE Office of Science Facility, at Brookhaven National Laboratory under contract no. DE-SC0012704. This research also used computational resources of the University of Chicago’s Research Computing Center. This research additionally used resources of the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under Contract no. DE-AC02-05CH11231. The authors would like to thank R. Farber for helpful discussions in processing STM images.

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Author notes

  1. These authors contributed equally: Dongho Lee, Wennie Wang, Chenyu Zhou.

Authors and Affiliations

  1. Department of Chemistry, University of Wisconsin–Madison, Madison, WI, USA

    Dongho Lee & Kyoung-Shin Choi

  2. Pritzker School of Molecular Engineering, University of Chicago, Chicago, IL, USA

    Wennie Wang & Giulia Galli

  3. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, USA

    Chenyu Zhou, Xiao Tong & Mingzhao Liu

  4. Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY, USA

    Chenyu Zhou

  5. Department of Chemistry, University of Chicago, Chicago, IL, USA

    Giulia Galli

  6. Argonne National Laboratory, Lemont, IL, USA

    Giulia Galli

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Contributions

K.-S.C., G.G. and M.L. supervised the combined experimental and computational investigations. C.Z. prepared epitaxial BiVO4 and performed STM imaging and LEIS analysis of BiVO4 together with X.T. under the supervision of M.L. D.L. performed all other experimental studies of BiVO4 under the supervision of K.-S.C. W.W. performed all computational calculations under the supervision of G.G. All authors discussed the results and contributed to writing the manuscript.

Corresponding authors

Correspondence to Mingzhao Liu, Giulia Galli or Kyoung-Shin Choi.

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The authors declare no competing interests.

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Peer review information Nature Energy thanks Fatwa Abdi, Ian Sharp and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–13, Table 1 and references.

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Lee, D., Wang, W., Zhou, C. et al. The impact of surface composition on the interfacial energetics and photoelectrochemical properties of BiVO4. Nat Energy 6, 287–294 (2021). https://doi.org/10.1038/s41560-021-00777-x

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