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Article Abstract
Photoelectrochemical cathodic protection (PECCP) is a novel and environment-friendly metal anti-corrosion technology, and constructing photoelectronic materials that can provide sustained protection under both illumination and dark is a key challenge. Herein, four cases of transition metal (TM) and carboxyltin-modified polyoxometalates (POMs) based on trivacant Keggin-type tungstobismuthate subunits, denoted as Bi-POMs, were designed and synthesized in aqueous solutions. The introduced carboxyl groups can anchor TiO, and the export of electrons from POM clusters occurred, making these POM-based materials useable in the PECCP field for the first time. Under illumination, the Bi-POM/TiO photoanodes were capable of cathodically polarizing 304 stainless steel (304SS) by 440-465 mV. In darkness, their coupled potentials of -197 to -175 mV were significantly lower than that of TiO (-97 mV), indicating the obviously enhanced dark cathodic protection effect. Precisely, the interdependence between Bi, POM, and TiO ensures Bi-POMs to protect 304SS in seawater and provide stable and sustainable cathodic protection under intermittent light. The underlying mechanisms of PECCP were explored by a variety of experimental techniques including the femtosecond transient absorption (fs-TA) measurements and density functional theory (DFT) calculations. The integration of POMs into the PECCP system represents a new insight in the development of green metal protection technologies.
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| http://dx.doi.org/10.1002/chem.202501319 | DOI Listing |
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