Search

Severe marine metallic corrosion urges extensive research on corrosion protection methods. Environment-friendly photoelectric cathodic protection (PCP) technology for marine metallic corrosion adopting abundant solar light in ocean was developed speedily. Particularly, photoelectric materials with dark-state sustained cathodic protection performance are worthy of further studies in pursue of the long-term PCP. Based on nanoarchitectonics strategy, together with the integration of electron storage materials, herein, an environment-friendly network-like SnIn4S8/TiO2 photoelectrode with electron storage capability was constructed. The flower-like SnIn4S8 with variable valence indium was compounded in situ on the ultrafine branched TiO2 substrate and formed a dual network-like SnIn4S8/TiO2 architecture. Its larger electrochemical surface area and electric double layer capacitance, and the reversible valence variation of In3+/In+, gives full play of the storage and release of photogenerated electrons. SnIn4S8-15h/TiO2 photoelectrode offered photogenerated electrons to the coupled pure copper (Cu) electrode with electric quantity of 3401 µC under the simulated sunlight irradiation of 50 s, and sustainedly offered the stored photogenerated electrons to it with 1390 µC in the dark. Contrastively, single TiO2 or SnIn4S8 did not show sustained PCP performance. The multiple architecture characteristics make SnIn4S8-15h/TiO2 show enhanced PCP and sustained cathodic protection performance for Cu and 316 L stainless steel (SS) both under light illumination and in the dark. Polysulfide SnIn4S8 pulls the potential toward negative direction which benefits the PCP for more kinds of metals in 3.5 wt% NaCl solution (a simulated marine environment) without hole scavenger added. This work provides insights in the solar light-driven sustained PCP application. [ABSTRACT FROM AUTHOR]

The global annual consumption of marine metal corrosion is a significant challenge to the service life of metals and the development of marine strategies. A tri-dimensional AgInS2/In2S3 co-modified TiO2 nanobush (NB) superstructure photoanode is constructed. It shows superior photoelectric cathodic protection (PECP) characteristic for pure copper whose self-corrosion potential is more negative in simulated natural marine environment without additional any hole scavengers under simulated solar light illumination. Origin from the more negative energy level potential of AgInS2/In2S3, the quasi-Fermi level of the photogenerated electrons of TiO2 NB/AgInS2/In2S3 was pull to a more negative position, reinforcing the transmission of photogenerated electrons to the pure copper whose self-corrosion potential is more negative. The sensitizer AgInS2 together with the assistant layer In2S3 dramatically enhances the PECP performance of TiO2 NB/AgInS2/In2S3. The tri-dimensional ultrafine branch-like architecture of TiO2 NB with the nanoparticles quickens the collection and transfer of photogenerated electrons to the metallic pure copper. This environmentally friendly 3D photoanode structure provides a good reference for the optimized construction of photoelectric materials for marine metal corrosion protection. The tri-dimensional AgInS2/In2S3 co-modified TiO2 nanobush superstructure photoanode possesses superior photoelectric cathodic protection characteristic for pure cooper whose self-corrosion potential is more negative in simulated marine environment under simulated solar light illumination. [ABSTRACT FROM AUTHOR]

• 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]