Green synthesis of magnetic azo-linked porous organic polymers with recyclable properties for enhanced Bisphenol-A adsorption from aqueous solutions.

Porous organic polymers (POPs) present superior adsorption performance to steroid endocrine disruptors. However, the effective recovery and high cost have been a big limitation for their large-scale applications. Herein, magnetic azo-linked porous polymers (Fe3O4@SiO2/ALP-p) were designed and prepared in a green synthesis approach using low-price materials from phloroglucinol and pararosaniline via a diazo-coupling reaction under standard temperature and pressure conditions, which embedded with Fe3O4@SiO2 nanoparticles to form three-dimensional interlayer network structure with flexible-rigid interweaving. The saturated adsorption capacity to bisphenol-A (BPA) was 485.09 mg/g at 298 K, which increased by 1.4 times compared with ALP-p of relatively smaller mass density. This enhanced adsorption was ascribed to increment from surface adsorption and pore filling with 2.3 times of specific surface area and 2.6 times of pore volume, although the total organic functional groups decreased with Fe3O4@SiO2 amendment. Also, the adsorption rate increased by about 1.1 and 1.5-fold due to enhancement in the initial stage of surface adsorption and subsequent stage pore diffusion, respectively. Moreover, this adsorbent could be used in broad pH (3.0-7.0) and salinity adaptability (<0.5 mol/L). The loss of adsorption capacity and magnetic recovery were lower than 1.1% and 0.8% in each operation cycle because of the flexible-rigid interweave. This excellent performance was contributed by synergistic effects from physisorption and chemisorption, such as pore filling, electrostatic attraction, π-π stacking, hydrogen bonding, and hydrophobic interaction. This study offered a cost-effective, high-performing, and ecologically friendly material along with a green preparation method.

Design and preparation of functional azo linked polymers for the adsorptive removal of bisphenol A from water: Performance and analysis of the mechanism.

In order to effectively remove refractory bisphenol A (BPA) from water, a novel nitrogen doped organic porous functional azo linked polymer (ALP-p) was designed and prepared according to the physicochemical characteristics of propane linked to two phenol hydroxyl groups. This ALP-p was synthesized with 98.5% yield, from pararosaniline and phloroglucinol, via the diazo coupling reaction to produce multiple adsorption functional groups of benzene ring, hydroxyl group and azo group. This functional material showed high adsorption capacity of 357.8 mg/g for 50 mg/L BPA, at 20 °C. The adsorption kinetics and isotherms were described by the pseudo-second-order and Langmuir model, respectively. The major adsorption mechanisms were attributed to the high specific surface area (259.8 m2/g) and pore volume (0.56 cm3/g) related surface adsorption and pore diffusion through porous stereoscopic stacking cavity anchorage. The functional group from the three-dimensional skeleton structures of ALP-p for BPA anchoring endowed chemisorption via π-π interaction between benzene rings and hydrogen-bonding (O-H⋯O, C-H⋯N, C-H⋯O and C-H⋯C) with the hydrogen atom of benzene ring, -OH from BPA and -OH, NN from ALP-p, respectively. The coexisting organic pollutants and alkali environment posed a negative effect on adsorption, while salinity had no significant effect on the process. The adsorption capacity and recovery of ALP-p were >93.5% and 81.6% after five cycles of operation.