Development of anti-corrosive coating on AZ31 Mg alloy modified by MOF/LDH/PEO hybrids

The self-assembly of hybrid inorganic-organic materials on stationary platforms plays a critical role in improving their structural stability and wide usability. In this work, a novel two-step hydrothermal approach is proposed for synthesizing stable and advanced hybrid coatings on metal-oxide platforms through the surface modification of layered double hydroxide (LDH) films using novel metal-organic frameworks (MOFs). Initially, Mg-Al LDH nanocontainers, grown on a magnesium oxide layer produced through plasma electrolytic oxidation (PEO) of AZ31 Mg alloy substrate, were intercalated with cobalt via an oxidation route, providing the metallic coordination center for the MOF formation. In the subsequent step, a pioneering technique is introduced, utilizing tryptophan as the organic linker for the first time at a pH of 10. The self-assembly of cobalt- tryptophan complex, driven by the strong bonding between electrophilic sites of monomers and nucleophilic sites, facilitated the formation of a MOF network having a cloud-like structure on the surface of MgAl LDH’s film. The resulting MOF-LDH encapsulation containers demonstrate exceptional electrochemical stability when exposed to a 3.5 wt.% NaCl solution, surpassing the performance of PEO and pure LDH coatings. This enhanced stability is attributed to the development of a dense top layer and a stable composition within the self-assembled MOF, effectively sealing flaws and preventing the infiltration of corrosive ions into the underlying metallic substrate. The formation mechanism of MOFs on LDH galleries is investigated using density functional theory calculations.