NiFe Prussian blue analog cocatalyzed TiO₂/In₂S₃ type-II heterojunction for solar water splitting

Abstract

Due to the excellent stability of titanium dioxide (TiO₂), there is still value in improving its solar-to-hydrogen conversion efficiency through tremendous attempts. Metal sulfides with a narrow bandgap are good candidates to broaden the ultraviolet light absorption of TiO₂ into the visible light region. However, sulfides suffer from the photocorrosion issue, leading to poor stability. Herein, a type-II heterojunction of TiO₂/In₂S₃ is fabricated by a hydrothermal method, and a NiFe Prussian blue analog (NFP) overlayer is deposited on the surface of TiO₂/In₂S₃ through a chemical bath deposition technique. Under AM1.5G illumination, a photocurrent density of 1.81 mA cm^-2 can be obtained with NFP coated TiO₂/In₂S₃ at 1.23 V vs. reversible hydrogen electrode, which is six folds of the photocurrent of TiO₂. This photocurrent value can reach up to about 90% of its theoretical photocurrent. During a 12 h stability test, the TiO₂/In₂S₃/NFP photoanode exhibits a high photocurrent retention of 95.17% after an initial transient decrease. The type-II heterojunction of TiO₂/In₂S₃ can efficiently boost the charge separation because of the built-in electric field and enhance the visible-light absorption because of the narrow bandgap of In₂S₃. A NFP overlayer serves as the cocatalyst for water oxidation reaction due to its valence changes of nickel and iron elements. NFP cocatalyst can rapidly extract the photogenerated holes from In₂S₃ and then improve the charge separation/injection efficiencies. Thanks to chemical stability of NFP, its coating can also make In₂S₃ resistant to photocorrosion by physically separating the photoanode from the electrolyte. Therefore, there is a good synergistic effect between the TiO₂/In₂S₃ heterojunction and NFP cocatalyst. This work provides some crucial insights for the interface engineering and material design in photoelectrochemical systems.

Keywords

Solar water splitting / heterojunction / cocatalyst / Prussian blue analog / indium sulfide

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