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Buffer effect of In2O3 interlayer on band offset at CuO/ZnO interface for enhanced photoelectrocatalytic water splitting

Chen, Ying-Chu, Wu, Zhi-Jie, Hsu, Yu-Kuei
Journal of catalysis 2019 v.370 pp. 224-231
X-ray photoelectron spectroscopy, chemical composition, cupric oxide, electric current, nanocrystals, photocatalysis, synergism, transmission electron microscopy, zinc oxide
Multiple heterojunction made of CuO nanocrystals building on ZnO scaffold buffered by an In2O3 interlayer is fabricated through simple wet chemistry. Scanning and transmission electron microscopy reveal this CuO/In2O3/ZnO heterojunction forming multi-core-shell nanostructure. X-ray photoelectron spectroscopy is performed to analyze the chemical compositions. Such system is further employed in sunlight-driven photoelectrochemical water splitting, wherein Mott-Schottky analysis demonstrates its flat-band potential negatively shifted. This originates from the lower electron affinity of CuO compared to that of ZnO, favoring photocurrent generation at early onset potential. More importantly, the entire gamut of visible-light is harnessed by CuO, as manifested in the photocurrent action spectrum. Last but not least, the charge-separation is promoted at the In2O3 interface, as reflected in the impedance measurement. The synergistic effect endows the CuO/In2O3/ZnO photoelectrode with the highest photocurrent of 1.22 mA⋅cm−2 (at ∼1.6 V vs. RHE) that outperforms those of the CuO/ZnO and ZnO photoanodes, respectively.