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Inter-facet junction effects on particulate photoelectrodes

Nature Materials volume 21, pages 331–337 (2022)Cite this article

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Abstract

Particulate semiconductor photocatalysts are paramount for many solar energy conversion technologies. In anisotropically shaped photocatalyst particles, the different constituent facets may form inter-facet junctions at their adjoining edges, analogous to lateral two-dimensional (2D) heterojunctions or pseudo-2D junctions made of few-layer 2D materials. Using subfacet-level multimodal functional imaging, we uncover inter-facet junction effects on anisotropically shaped bismuth vanadate (BiVO4) particles and identify the characteristics of near-edge transition zones on the particle surface, which underpin the whole-particle photoelectrochemistry. We further show that chemical doping modulates the widths of such near-edge surface transition zones, consequently altering particles’ performance. Decoupled facet-size scaling laws further translate inter-facet junction effects into quantitative particle-size engineering principles, revealing surprising multiphasic size dependences of whole-particle photoelectrode performance. The imaging tools, the analytical framework and the inter-facet junction concept pave new avenues towards understanding, predicting and engineering (opto)electronic and photoelectrochemical properties of faceted semiconducting materials, with broad implications in energy science and semiconductor technology.

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Fig. 1: Visualizing inter-facet junction effects in anisotropically shaped semiconductor particles.
Fig. 2: Inter-facet junctions govern whole-particle photoelectrochemistry.
Fig. 3: Engineering inter-facet junctions via chemical doping to modulate photoelectrode performance.
Fig. 4: Translating inter-facet junction effects into size engineering principles of shaped particles.

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All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Information.

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MATLAB codes for data analysis and simulations supporting the findings of this study are provided with this paper.

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Acknowledgements

This research was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Science program, under award DE-SC0004911. It used Cornell Center for Materials Research shared facilities supported by NSF (grant no. DMR-1120296). We thank M. Hesari, N. Zou, G. Chen and W. Jung for discussions on experiment and data analysis.

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  1. Xianwen Mao

    Present address: Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore

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  1. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA

    Xianwen Mao & Peng Chen

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Contributions

X.M. and P.C. designed research. X.M. synthesized materials, constructed instrument, performed measurements, coded software and analysed data. X.M. and P.C. discussed results and wrote the manuscript.

Corresponding author

Correspondence to Peng Chen.

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Competing interests

X.M. and P.C. has filed a provisional patent (US Provisional Application no. 63/136,703) based on this work. This patent, entitled ‘Materials and methods enabling two-dimensional junctions on three-dimensional particles’, was filed with the US Patent and Trademark Office on 13 January 2021.

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Peer review information Nature Materials thanks Shannon Boettcher, Patrick Unwin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–19, Discussion and Table 1.

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Mao, X., Chen, P. Inter-facet junction effects on particulate photoelectrodes. Nat. Mater. 21, 331–337 (2022). https://doi.org/10.1038/s41563-021-01161-6

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