Research progress of TiO2 photocathodic protection to metals in marine environment

Corrosion protection has become an important issue as the amount of infrastructure construction in marine environment increased.Photocathodic protection is a promising method to reduce the corrosion of metals,and titanium dioxide(TiO2) is the most widely used photoanode.This review summarizes the progress in TiO2 photo gene rated protection in recent years.Different types of semiconductors,including sulfides,metals,metal oxide s,polymers,and other materials,are used to design and modify TiO2.The strategy to dramatically improve the efficiency of photoactivity is proposed,and the mechanism is investigated in detail.Characterization methods are also introduced,including morphology testing,light absorption,photoelectrochemistry,and protected metal observation.This review aims to provide a comprehensive overview of Ti02 development and guide photocathodic protection.

Directing the photogenerated charge flow in a photocathodic metal protection system with single-domain ferroelectric PbTiO_(3)nanoplates

Photocathodic protection(PCP)is arguably an ideal alternative technology to the conventional electrochemical cathodic protection methods for corrosion mitigation of metallic infrastructure due to its eco-friendliness and low-energy-consumption,but the construction of highlyefficient PCP systems still remains challenging,caused primarily by the lack of driving force to guide the charge flow through the whole PCP photoanodes.Here,we tackle this key issue by equipping the PCP photoanode with ferroelectric single-domain PbTiO_(3)nanoplates,which can form a directional“macroscopic electric field”throughout the entire photoanode controllable by external polarization.The properly poled PCP photoanode allows the photogenerated electrons and holes to migrate in opposite directions,that is,electrons to the protected metal and holes to the photoanode/electrolyte interface,leading to largely suppressed charge annihilation and consequently a considerable boost in the overall solar energy conversion efficiency of the PCP system.The as-fabricated photoanode can not only supply sufficient photocurrent to 304 stainless steel to initiate cathodic protection,but also shift the metal potential to the corrosion-free range.Our findings provide a viable design strategy for future high-performance PCP systems based on ferroelectric nanomaterials with enhanced charge flow manipulation.

Characterization and photoelectrochemical performance of Zn-doped TiO_2 films by sol-gel method

Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, photocathodic protection and photoelectrochemical properties of TiO2 thin films were investigated. It is indicated that the photoelectrical performance of the Zn?TiO2 films is enhanced with the addition of Zn element compared with the pure-TiO2 film and the largest decline by 897 mV in the electrode potential is achieved under 300 °C heat treatment. SEM?EDS analyses show that Zn element is unevenly distributed in Zn?TiO2 films; XRD patterns reveal that the grain size of Zn?TiO2 is smaller than that of pure-TiO2; FTIR results indicate that Zn - O bond forms on Zn?TiO2 surface. Ultraviolet visible absorption spectra prove that Zn?TiO2 shifts to visible light region.Mott?Shottky curves show that the flat-band potential of Zn?TiO2 is more negative and charge carrier density is bigger than that ofpure-TiO2, implying that under the synergy of the width of the space-charge layer, carrier density and flat-band potential, Zn?TiO2 with 300 °C heat treatment displays the best photocathodic protection performance.

Preparation of Ag@CuFe_(2)O_(4)@TiO_(2) nanocomposite films and its performance of photoelectrochemical cathodic protection

A Ag@CuFe_(2)O_(4)@TiO_(2) nanocomposite film with high performance of photogenerated cathodic protection was prepared by hydrothermal and photoreduction methods.The results showed that when the CuFe_(2)O_(4) hydrothermal reaction time was 6 h and the AgNO_(3) concentration was 0.1 M,the Ag@CuFe_(2)O_(4)@TiO_(2) nanocomposite material performed the best cathodic protection capability for 304 stainless steel(304SS).In this case,the protective potential achieved-930 mV(versus SCE)associated with the photocurrent density of 475μA/cm^(2),which was 14.8 times that of pure TiO_(2) nanowires.In the dark,the nanocomposite provided cathodic protection of up to 485 mV for 304SS.Due to the heterogeneous junctions at the two interfaces among the three kinds of nanocomposite materials,the build-in electric field was fabricated,which promoted the separation efficiency of photogenerated electrons and holes and effectively improved the photochemical cathodic protection of 304SS.

One-dimensional Ag2S/ZnS/ZnO nanorod array films for photocathodic protection for 304 stainless steel

Highly ordered Ag2 S/ZnS/ZnO nanorod array film photoanodes were prepared on a Ti substrate for photocathodic cathodic protection.The results indicated that the photoresponse range of the Ag2S/ZnS/ZnO composite film was extended compared to those of the ZnO and ZnS/ZnO films,indicating its higher light absorption capacity.When the Ag2S/ZnS/ZnO composite film served as a photoanode,the film can provide the best effective photocathodic protection for 304 stainless steel in a 3.5 wt%NaCl solution under white light illumination compared to the ZnO and ZnS/ZnO films.Additionally,in comparison to pure ZnO film,the photocurrent for the ZnS/ZnO film remained the same without noticeable fluctuation after illumination for 1 h,indicating that the ZnS functionalization improved the stability by overcoming the photocorrosion effect of the ZnO photoanode under light irradiation.

Constructing Bi_(2)WO_(6)-decorated TiO_(2) composite films for photocathodic protection of 304 stainless steel

Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire and Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire composite films were successfully prepared using a hydrothermal method.The results show that the light absorption for Bi_(2)WO_(6)/TiO_(2) composite films is extended to the visible region after Bi_(2)WO_(6) nanoplates and nanoflowers are assembled onto TiO_(2) nanowires.Furthermore,Bi_(2)WO_(6) nanoflower/TiO_(2) nano wire composite film exhibits a better absorption property compared to Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire film,which is mainly ascribed to the narrower bandgap of Bi_(2)WO_(6) nanoflower compared to that of Bi_(2)WO_(6) nanoplate.The photocurrent density for Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire and Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire composite films can reach 95 and 62.5 μA cm-2,respectively,which are much higher than that obtained for a pure TiO_(2) nanowire film(25 μA cm-2).Meanwhile,under illumination,the pure TiO_(2) nanowire,Bi_(2)WO_(6) nanoplate/TiO_(2) nanowire and Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire films can reduce the potential of the coupled 304 stainless steel in 3.5 wt.%NaCl solution by 299,719 and 739 mV,respectively.Thus,Bi_(2)WO_(6) nanoflower/TiO_(2) nanowire film is found to provide the best effective photocathodic protection for 304 stainless steel.This work not only provides an example of shape-dependent photocathodic protection based on Bi_(2)WO_(6) but also opens up new possibilities to design an ideal microstructure on the basis of semiconductor materials for future applications of photocathodic protection.