Molecularly Engineered Aza-Crown Ether Functionalized Sodium Alginate Aerogels for Highly Selective and Sustainable Cu2+ Removal

Developing sustainable and molecularly selective adsorbents for heavy-metal removal remains a critical challenge in water purification. Herein, we report a green molecular-engineering approach for fabricating aza-crown ether functionalized sodium alginate aerogels (ACSA) capable of highly selective Cu²⁺ capture. The aerogels were synthesized via saccharide-ring oxidation, Cu²⁺-templated self-assembly, and reductive amination, enabling the covalent integration of aza-crown ether motifs within a hierarchically porous biopolymer matrix. Structural analyses (FTIR, ¹³C NMR, XPS, SEM, TGA) confirmed the in situ formation of macrocyclic N/O coordination sites. Owing to their interconnected porosity and chemically stable framework, ACSA exhibited rapid sorption kinetics following a pseudo-second-order model (R² = 0.999) and a Langmuir maximum adsorption capacity of 150.82 mg·g^-1. The material displayed remarkable Cu²⁺ selectivity over Zn²⁺, Cd²⁺, and Ni²⁺, arising from the precise alignment between Cu²⁺ ionic radius (0.73 Å) and crown-cavity dimensions, synergistic N/O chelation, and Jahn-Teller stabilization. Over four regeneration cycles, ACSA retained more than 80% of its original adsorption capacity, confirming excellent durability and reusability. This saccharide-ring modification strategy eliminates crown-ether leaching and weak anchoring, offering a scalable and environmentally benign route to bio-based adsorbents that combine molecular recognition with structural stability for efficient Cu²⁺ remediation and beyond.