H₂O₂-Triggered Rapid Deposition of Poly(caffeic acid) Coatings: A Mechanism-Based Entry to Versatile and High-Efficient Molecular Separation

Plant-derived polyphenol coating offers a promising route to fabricate functional surfaces for different substrate materials. However, almost all of the deposition approaches are time-consuming and involve inefficient processes, and the mechanisms behind the coating deposition are rarely understood. Herein, we report a rational methodology to achieve the rapid deposition of poly(caffeic acid) (PCA) by using H2O2 as a trigger under the assistance of copper sulfate (CuSO4). The comparative monomer structure of PCA oxidation polymerization has illustrated a significant distinction in the reaction path for PCA coating deposition which has never been reported before. Until now, the unprecedented fast velocity for polyphenol coating has been obtained, and the PCA coating exhibits excellent homogeneity, spatiotemporal tunability, and firm stability. Moreover, three different types of filtration membranes, poly(vinylidene fluoride) microfiltration membrane (PVDF MF membrane), poly(ether sulfone) (PES) ultrafiltration (UF) hollow fiber membrane, and PCA-coated PES nanofiltration (NF) membrane, are all successfully dip-coated using H2O2-triggered PCA coating. Without synthetic complexities and intricate procedures, the formation of hydrophilic and homogeneous PCA aggregates on the surface and/or inside pore walls resulted in various membranes. The as-prepared PCA-coated PVDF MF membrane demonstrates excellent oil/water separation efficiency of less than 150 ppm and a flux recovery rate of approximately 90% even after five cycles. By one-step co-deposition of PCA and poly(2-ethyl-2-oxazoline) (PEtOx) on the PES UF membrane surface, hydrophilicity and biofouling resistance are implemented for efficient protein filtration. The PES NF membrane formed by the PCA layer exhibits high mono-/divalent ion selectivity and excellent chlorine resistance. Overall, these results represent a rapid and sustainable approach to tailor PCA coatings for versatile liquid separation processes.