Preparation and properties of double-template magnetic molecularly imprinted polymers for removal of nitrophenol from drinking water

Abstract

In order to efficiently remove 4-nitrophenol (4-NP) and 2,4-dinitrophenol (2,4-DNP), 4-NP and 2,4-DNP were used as template molecules and double-template magnetic molecularly imprinted polymers (D-MIPs) were prepared by surface molecular imprinting technology using itaconic acid as functional monomer, Fe₃O₄@SiO₂ as carrier, ethylene glycol dimethacrylate as crosslinking agent and azodiisobutyronitrile as initiator. The morphology of D-MIPs was characterized using FT-IR and SEM. The adsorption specificity, regenerability, and applicability of D-MIPs were studied in detail. The results show that D-MIPs successfully coated the surface of the Fe₃O₄@SiO₂ carrier and had a good polymerization effect, specific recognition sites, and good imprinting performance, with a diameter of 90 nm and homogeneous shape. The theoretical adsorption capacities of 4-NP-MIPs, 2, 4-DNP-MIPs, and D-MIPs for target molecules were 103.97, 73.14 and 123.99 mg/g, respectively. There were many adsorption sites with different adsorption energies. D-MIPs reached the optimal adsorption equilibrium state in 30 min. The best fitting models for the MIPs were the Freundlich adsorption and pseudo-second-order kinetic models, indicating that adsorption of MIPs occurred via a chemical adsorption process. Test results show that MIPs had highly specific recognition and selective adsorption capacity in different water samples. After eight regeneration cycles, the adsorption capacity of D-MIPs decreased by 7.51%, confirming that MIPs had excellent regeneration.

Keywords

4-nitrophenol / 2,4-dinitrophenol / double template / molecularly imprinted polymers / adsorption performance

References

[[1]] Dhanasekaran T, Manigandan R, Padmanaban A, et al.. Fabrication of Ag@Co-Al layered double hydroxides reinforced poly(o-phenylenediamine) nanohybrid for efficient electrochemical detection of 4-nitrophenol, 2,4-dinitrophenol and uric acid at nano Molar level [J]. Scientific Reports, 2019, 9(1): 13250, pmcid: 6744444

[[2]] Wu H-H, Zu F-H, Fu S, et al.. Ag@Silsequioxanes: Synthesis and its catalytic reduction performance for p-Nitrophenol [J]. Chinese Journal of Inorganic Chemistry, 2021, 37(11): 1961-1969

[[3]] Ren X-F, Qi Y-E, Jin X-Q, et al.. Co/Fe-Catalyzed reduction of 4-nitrophenol with sodium borohydride in water [J]. Chemistry & Bioengineering, 2019, 36(11): 20-25

[[4]] Ji Y-F, Shi Y-Y, Yang Y, et al.. Rethinking sulfate radical-based oxidation of nitrophenols: Formation of toxic polynitrophenols, nitrated biphenyls and diphenyl ethers [J]. Journal of Hazardous Materials, 2019, 361: 152-161,

[[5]] Abaide E R, Dotto G L, Tres M V, et al.. Adsorption of 2-nitrophenol using rice straw and rice husks hydrolyzed by subcritical water [J]. Bioresource Technology, 2019, 284: 25-35,

[[6]] He Q, Liang J-J, Chen L-X, et al.. Removal of the environmental pollutant carbamazepine using molecular imprinted adsorbents: Molecular simulation, adsorption properties, and mechanisms [J]. Water research, 2020, 168: 115164,

[[7]] Dai Y, Wang X-C, Zheng Y-N, et al.. Research progress of molecular imprinting technology in the life science [J]. Biological Chemical Engineering, 2022, 8(3): 159-161

[[8]] Yan Z, Fang G-Z. Molecularly imprinted polymer based on upconversion nanoparticles for highly selective and sensitive determination of Ochratoxin A [J]. Journal of Central South University, 2019, 26(3): 515-523,

[[9]] Wagn J, Hou G-Y, Wu L-K, et al.. A novel adsorbent of three-dimensional ordered macro/mesoporous carbon for removal of malachite green dye [J]. Journal of Central South University, 2020, 27(2): 388-402,

[[10]] Xiao J-J, Yao C, Wu Y-X, et al.. Adsorption and flotation mechanism of a ketoxime-dithiocarbonate surfactant to chalcopyrite [J]. Journal of Central South University, 2022, 29(12): 3847-3857,

[[11]] Tang J, Liu G-H, Qi T-G, et al.. Fibrous activated alumina prepared through phase transformation using dawsonite as a template [J]. Journal of Central South University, 2022, 29(4): 1147-1160,

[[12]] Zhu F, Lu H-J, Lu Y-H. Effective solid phase extraction for the enrichment of p-nitrophenol in water using microwave-assisted synthesized fly ash@ p-nitrophenol surface molecular imprinted polymer [J]. Journal of Materials Science, 2023, 58(10): 4399-4415,

[[13]] Zhu F, Li L-W, Li N, et al.. Selective solid phase extraction and preconcentration of Cd(II) in the solution using microwave-assisted inverse emulsion-suspension Cd (II) ion imprinted polymer [J]. Microchemical Journal, 2021, 164: 106060,

[[14]] Li N, Lu H-J, Liang Y-K, et al.. Microwave-assisted magnetic Cu(II)-imprinted-polymer based on double functional monomers for selective removal of Cu(II) from Wastewater [J]. Journal of Water Chemistry and Technology, 2022, 44(6): 431-439,

[[15]] Gubin A S, Sukhanov P T, Sannikova N Y, et al.. Use of molecularly imprinted polymer for the preconcentration of 4-nitrophenol from aqueous media [J]. Journal of Analytical Chemistry, 2019, 74(S1): 11-17,

[[16]] Tian L, Jiang H-L J, Chen P-H, et al.. A novel GO/PNIPAm hybrid with two functional domains can simultaneously effectively adsorb and recover valuable organic and inorganic resources [J]. Chemical Engineering Journal, 2018, 343: 607-618,

[[17]] Zhou X-X, Lai C, Huang D-L, et al.. Preparation of water-compatible molecularly imprinted thiolfunctionalized activated titanium dioxide: Selective adsorption and efficient photodegradation of 2, 4-dinitrophenol in aqueous solution [J]. Journal of Hazardous Materials, 2018, 346: 113-123,

[[18]] Gao Y. . Study on 4-nitrophenol molecularly imprinted polymer’s synthetic methods and characteristics [D], 2019 Chuzhou, China Anhui University of Technology (in Chinese)

[[19]] Yu W-N. . Preparation of two Phenolic Surface Imprinted Polymers and their Application in Environmental Analysis [D], 2017 Xinxiang, China Henan Normal University (in Chinese)