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Microstructure evolution with composition ratio in self-assembled WO3–BiVO4 hetero nanostructures for water splitting

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Abstract

A series of self-assembled WO3–BiVO4 nanostructured thin films with 17, 25, 50, 67, and 100 mol% WO3 were grown on the (001) yttria-stabilized zirconia (YSZ) substrate by pulsed laser deposition method. The microstructures including crystalline phases, epitaxial relationship, interface structures, and chemical composition distributions were investigated by a combination of various electron microscopy techniques including scanning electron microscopy, transmission electron microscopy, and X-ray energy dispersive spectroscopy. The monoclinic BiVO4 formed the matrix, in which WO3 nanopillars were embedded with specific epitaxial relationships. In BiVO4-rich sample, orthorhombic Bi2WO6 was formed. However, metastable hexagonal WO3 phase and orthorhombic WO3 phase coexisted in other composite samples. The thin amorphous layer at the film/substrate interface indicated that the mismatch strain between films and substrate is released. The hydrostatic tensile strain due to thermal expansion mismatch between BiVO4 and WO3 as well as the diffusion of Bi into the WO3 stabilized the metastable h-WO3. A WO3–BiVO4 pseudobinary phase diagram was proposed based on the magnitude of the thermal expansion mismatch and the distance of Bi diffusion, which can be applied to design the microstructures of WO3–BiVO4 heterojunctions and optimize their photoelectrochemical properties.

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ACKNOWLEDGMENTS

This work was supported by the National Key Project for Basic Research of China (Grant Nos. 2014CB921104 and 2013CB922301), NSFC under Grant No. 51572085, and Natural Science Foundation of Shanghai (16ZR1409500).

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Authors and Affiliations

  1. Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai, 200241, China

    Haili Song, Chao Li, Ruijuan Qi, Rong Huang & Chun-Gang Duan

  2. Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu, 30010, Taiwan

    Chien Nguyen Van & Ying-Hao Chu

  3. Department of Material Science and Engineering, National Chung Hsing University, Taichung, 402, Taiwan

    Heng-Jui Liu

  4. Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan, Shanxi, 030006, China

    Rong Huang & Chun-Gang Duan

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  1. Haili Song
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Correspondence to Rong Huang.

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Song, H., Li, C., Van, C.N. et al. Microstructure evolution with composition ratio in self-assembled WO3–BiVO4 hetero nanostructures for water splitting. Journal of Materials Research 32, 2790–2799 (2017). https://doi.org/10.1557/jmr.2017.250

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