Controlled Surface Engineering of Chitosan Hydrogels: Alkali/Urea Dissolution for Ratio-Specific Neodymium and Praseodymium Recovery

壳聚糖水凝胶的可控表面工程:碱/尿素溶解法实现钕和镨的特定比例回收

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Abstract

Rare earth elements (REEs) are critical for advanced technologies, with neodymium and praseodymium being essential to high-performance permanent magnets. The separation of these adjacent lanthanides represents a significant challenge due to their nearly identical chemical properties, with traditional chitosan surfaces exhibiting limited discrimination between chemically similar elements. Current separation methods require multiple processing steps and cannot maintain predetermined compositional ratios. Engineered polymer interfaces with controlled binding site distribution represents a critical advancement for selective separation, but achieving ratio-controlled extraction of adjacent elements remains challenging. Here, we demonstrate a novel interface engineering approach using alkali/urea dissolution to restructure chitosan networks, creating dual-template alkali/urea chitosan hydrogels (NdPr-AUCH) for simultaneous selective co-extraction of Nd(III) and Pr(III). We show that the dissolution-reformation process enables templated Nd:Pr selectivity ratios (1:1, 2:1, and 4:1) that directly correspond to synthesis compositions. NdPr-AUCH-11 achieved maximum uptake capacities of 19.85 mg/g for Nd(III) and 16.89 mg/g for Pr(III), while NdPr-AUCH-41 maintained 3.07:1 Nd:Pr selectivity in competitive environments. Thermodynamic analyses reveal consistently lower energy requirements for Nd(III) binding compared to Pr(III), demonstrating how interface engineering amplifies coordination differences between adjacent lanthanides. This work represents the first demonstration of ratio-controlled extraction of adjacent lanthanides within a single polymer matrix, advancing interface-engineered materials for selective rare earth recovery.

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