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• ZnIn 2 S 4 /TiO 2 nanoflowerbush photoanode was prepared by facile hydrothermal method. • The nanoflower-like ZnIn 2 S 4 was tightly incorporated on ultrafine branched TiO 2 NB. • The heterojunction greatly promotes the transfer of the photogenerated carriers. • ZnIn 2 S 4 /TiO 2 NFB exhibits photoinduced CP performance for metals in NaCl solution. [Display omitted] Boosting the photoinduced cathodic protection (CP) for metals in NaCl solution is crucial for achieving the application of photoelectrochemical conversion in marine corrosion protection. An environmentally friendly three-dimensional ZnIn 2 S 4 /TiO 2 nanoflowerbush (NFB) photoelectrode was constructed with sufficient interfacial incorporation based on the ultrafine branched TiO 2 nanobush substrate via a facile in situ hydrothermal method. This ZnIn 2 S 4 /TiO 2 NFB nanoheterojunction composite behaves excellent photoinduced CP performance for metallic materials. This is owing to the optimized construction of photoelectrode with relatively negative band potential, wide solar spectrum response, effective generation and collection of photoinduced electrons. The morphology, distribution and performance of ZnIn 2 S 4 vary with different substrates. The pure ZnIn 2 S 4 powder is nanoflower sphere composed of a lot of thin petals; when ZnIn 2 S 4 grow onto the FTO glass, the ZnIn 2 S 4 petals are distributed vertically on the two-dimensional structure; when ZnIn 2 S 4 grow on the three-dimensional ultrafine branched TiO 2 nanobush substrate, a ZnIn 2 S 4 /TiO 2 NFB architecture with ultrafine TiO 2 branchlet cores are formed. This ZnIn 2 S 4 /TiO 2 NFB photoelectrode can achieve efficient photoinduced CP performance for pure copper and low alloy steels with different negative self-corrosion potentials, such as Cu (−0.18 V), E40 (−0.45 V), Q345 (−0.55 V) and Q235 carbon steel (−0.65 V) under simulated sunlight irradiation in NaCl solution without additional hole scavengers, and the photoinduced CP current densities reach as high as 170, 72, 63 and 44 μA cm−2, respectively. The high-efficiency photoinduced CP performance is closely related to the band structure gradient matching between the TiO 2 and ZnIn 2 S 4 , prompting both the widened absorption of solar spectrum and high-efficiency transfer of the photogenerated electron–hole pairs. Importantly, the negative band potential of ZnIn 2 S 4 endues a lower surface work function which benefits the electron transport to the under-protected metallic materials to achieve photoinduced CP. This photoelectrode exhibits huge photoinduced CP application potential in marine environments. [ABSTRACT FROM AUTHOR]

• TiO 2 /MgTi x O y multiphase-heterojunction film was successfully prepared. • SKP is used to measure the surface work function of the photoelectrodes. • TiO 2 /MgTi x O y exhibits significantly enhanced PECCP Performance. • TiO 2 /MgTi x O y shows high PECCP stability. • The mechanism of TiO 2 /MgTi x O y multiphase heterojunctions for PECCP is proposed. Heterojunction engineering, as a rising star in the photoelectrochemical cathodic protection (PECCP) field, contributes to promote the separation of the photoinduced electrons and holes. In this paper, the TiO 2 /MgTi x O y multiphase-heterojunction film was prepared and its PECCP performance was studied. Due to a good energy band alignment gradient formed between the multiphases, the separation efficiency of the photoinduced electrons and holes generated by TiO 2 /MgTi x O y are dramatically enhanced, leading to its good PECCP performance and high stability. SKP is, for the first time, used to study the surface work function of the TiO 2 /MgTi x O y multiphase-heterojunction film for characterizing its PECCP performance. [ABSTRACT FROM AUTHOR]