Designing Phenolphthalein-Based Adsorptive Membranes for the High-Affinity, High-Capacity Capture of Contaminants...

The selective removal of solutes is crucial for ensuring a sustainable water supply, recovering resources, and cost-effective biomanufacturing. Adsorptive membranes are promising in this regard due to their rapid mass transfer and low energy demands. However, state-of-the-art adsorptive membranes offer limited pore sizes and surface chemistries. This study reports the development of adsorptive membranes from reactive phenolphthalein-based (PPH-based) polymers. These polymers, which are molecularly engineered to possess a high density of reactive pendant groups, are transformed into porous membranes through a surface-segregation vapor-induced phase separation (SVIPS) method. Examining the thermodynamic characteristics of the polymer-solvent-nonsolvent system informs the SVIPS manufacturing process and facilitates the formation of diverse membrane morphologies with hydraulic permeabilities ranging from 3400 to 13,500 L m^-2 h^-1 bar^-1. Copper ion binding experiments demonstrate a saturation capacity of 0.9 mmol Cu²⁺ g^-1, indicating high accessibility of the pendant groups for postsynthetic modification. Functionalization with alkyne groups enables one-step click reactions, such as the thiol-yne and Cu(I)-catalyzed azide-alkyne cycloaddition, expanding the membrane functionality. The incorporation of cucurbit[7]uril-azide macrocycles demonstrates the affinity-mediated capture of methyl viologen from solution. The combination of PPH-based polymers and the SVIPS method provides a versatile adsorptive membrane platform with a dense presentation of reactive sites, facilitating customization through diverse and high-yielding reactions.