A versatile, fast, and nature-inspired polyphenol chemistry surface modification was applied to prepare superhydrophobic surfaces with micro-grooved structures in this study. Tannic acid and iron ion (TA–FeIII) complexes were employed as a molecular building block for anchoring biomimetic coating onto the wood substrate with catalytically reducing formative Ag ions as the rough surface to ensure well-developed micro/nanostructure hierarchical roughness. TA–FeIII complexes also acted as stable bridges between the substrate and hydrophobic groups. The thickness and architecture of TA–FeIII complex coatings can be tailored by coordination-driven multistep assembly. The results indicated that the micro/nano hierarchical roughness structure was well-developed with increased coating times and increased deposition of reduced Ag nanoparticles, resulting in excellent superhydrophobic properties (e.g., water CA (contact angle) of about 156° and a rolling angle of about 4°). The superhydrophobic material exhibited outstanding stability and durability in harsh conditions, including strong acid/base or organic solvent, high-temperature water boiling, ultrasonic cleaning, and ultraviolet aging. A series of superhydrophobic models are proposed to clarify the effect of the micro/nano hierarchical structure on these superhydrophobic properties

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