Dual Stimulus Responsive GO-Modified Tb-MOF toward a Smart Coating for Corrosion Detection.

Abstract

Smart-sensing coatings that exhibit multistimulus response, rapid indication, and reusability are in urgent need to effectively enhance the practicability of coatings while accurately detecting metal corrosion. In this work, a reusable corrosion self-reporting coating with multiple pH and Fe3+ stimulus responses was first constructed by the integration of a composite fluorescent probe into the resin matrix. This composite sensor was constructed by combining a lanthanide metal-organic framework (Ln-MOF) based on terbium and trimeric acid (H3BTC) with graphene oxide (GO) nanosheets (GO@Tb-BTC). The incorporation of GO formed a sea-urchin-like structure, thereby increasing the specific surface area and active sites of the probe. The coatings were characterized by using electrochemical impedance spectroscopy (EIS), visual observation, and fluorescence spectrophotometry. The surface morphology, wettability, and adhesion of the coating samples were analyzed using SEM, XPS, hydrostatic contact angle test, and an adhesion test. EIS measurements in 3.5 wt % NaCl solution for 72 h demonstrated the superior corrosion protection performance of the 0.3 wt %/GO@Tb-BTC/WEP coating compared to blank coating, with the charge-transfer resistance reaching 4.33 × 107 Ω·cm2, which was 9.5 times higher than that of the pure coating. The bright green fluorescence of GO@Tb-BTC/WEP coating exhibited a turn-off response when there was an excess of OH-/H+, but it demonstrated a reversible turn-on fluorescence when the ambient pH returned to neutral. Furthermore, such Fe3+-triggered fluorescence quenching responded to concentrations as low as 1 × 10-6 M. The fluorescence quenching rate of both intact and damaged coatings surpassed that of visual and EIS detection methods. Significantly, the fluorescence in scratches was effectively quenched within 25 min using 0.3 wt %/GO@Tb-BTC/WPU coating for visual observation. GO@Tb-BTC demonstrated exceptional corrosion self-reporting capabilities in both epoxy and polyurethane systems, making it a versatile option beyond single-coating applications.