Novel benzylphosphate-based covalent porous organic polymers for the effective capture of rare earth elements from aqueous solutions

It has been a major challenge to develop stable and cost-effective porous materials that efficiently recover heavy rare earth elements (HREEs) due to ever-increasing demand, low availability and high cost of HREEs. This study presents two novel benzylphosphate-based covalent porous organic polymers (BPOP-1 and BPOP-2) that were prepared by facile one-pot Friedel-Crafts reactions. Various analytical techniques are used to investigate the successful syntheses of BPOP materials and establish their material properties, which include an unusual crystalline nature, large surface area, hierarchical pore structure, and superior chemical stabilities. The BPOPs effectively adsorb, and thus remove HREEs from aqueous media. In particular, BPOP-1 had higher phosphate content and exhibits superior adsorption capacities (Eu3+: 289.5; Gd3+: 292.7; Tb3+: 294.4; Dy3+: 301.9 mg/g) than BPOP-2, while BPOP-2 had higher mesoporosity and correspondingly supports faster adsorption kinetics. Remarkably, both BPOP materials exhibit some of the highest HREE adsorption capacities reported to date, the selective capture of Dy3+ ions, and excellent cyclic adsorption/desorption properties. We provide a potential adsorption mechanism for Dy3+ capture by the BPOP adsorbent. These demonstrate that introducing phosphate functionality into a robust porous polymer backbone with high surface area is a promising strategy for selective HREEs capture from wastewater.