Abstract
Solar energy-driven photoinduced cathodic protection (PICP) technology utilizes solar energy to protect marine metallic structures against severe marine corrosion. To enhance the solar energy utilization and strengthen dark-state application for realizing long-term protection, herein, a 3D nanothorn cluster-like WO3/ZnO/Zn-Bi2S3 multijunction with electron-storage characteristic and adjustable energy band was constructed. It exhibited an enhanced continuous release of photogenerated electron and sustained cathodic protection in dark conditions. Exposed to only 100 s of simulated sunlight irradiation, the WO3/ZnO/Zn-Bi2S3could store 5.27×10−2 C electrons and provide up to 5460 s of sustained CP for the coupled metal after light stops, which was 10.8 and 3.5 times higher than those of WO3/ZnO (4.89×10−3 C) and WO3/Zn-Bi2S3 (1.51×10−2 C), respectively. The WO3 nanothorn cluster-like substrate with reversible valence transformation of W6+/W5+ together with the large surface area and one-dimensional transmission path can store photogenerated electrons under illumination and release photogenerated electrons after light stops efficiently. Notably, the tri-phase heterojunction with introduction of intermediate “Carrier Springboard” ZnO between WO3 and Zn-Bi2S3 contributed to the building of well-matched energy band gradient to strengthen the directional backward transfer of photogenerated electrons and holes. The energy band of Bi2S3 sensitizer was adjusted towards negative direction by doping with zinc element to boost PICP application performance. The reversible valence transformation of Bi3+/Bi5+ could promote the consumption of photogenerated holes. These synergistically enhanced the sustained PICP performance of the WO3/ZnO/Zn-Bi2S3 photoelectrode both in dark and light conditions. This design shed light on energy-storage photoelectrodes for long-term PICP of metallic materials.
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