Unveiling the local structure of 2-mercaptobenzothiazole intercalated in (Zn2Al) layered double hydroxides

Abstract The structure and composition of a zinc‑aluminum layered double hydroxide (Zn2Al LDH) with the intercalated 2-mercaptobenzothiazole corrosion inhibitor (a.k.a. benzo[d]thiazole-2-thiol) are interpreted by means of atomistic molecular dynamics (MD) simulations. The results concerning the proportion of intercalated 2-mercaptobenzothiazole and water species in the Zn2Al LDH interlayer were correlated with experimental X-ray diffraction (XRD) and thermogravimetric analysis (TGA) data of samples obtained at pH 8.5, 10 and 11.5. While the sample synthesized at the lowest pH is almost free of contaminants, the sample obtained at the highest pH is contaminated by a small fraction of a material with intercalated OH−. The comparison of the calculated and XRD interlayer distances suggests that the most stable structure has a ratio of ~4.5 water molecules per intercalated organic species, which is higher than the ratio of ~2 typically reported in the literature. The distribution of molecules in the LDH interlayer consists of a layer of water near the hydroxides, a second layer grown over the first layer, with the 2-mercaptobenzothiazole species adopting conformations with the sulfur of the thioamide group facing the hydroxide/water layers and the 6-member ring oriented towards the middle of the interlayer. Different structural analyses were done to explain the equilibria between the different species in the interlayer space, and their molecular interactions with the LDH metal hydroxide layers.