Abstract: Porous polymers are very suitable materials for the adsorption of organic pollutants due to their abundant pores and organic frameworks in aqueous solution. However, their recovery from treated pollutant is difficult, and thus, their application is limited. A facile strategy to synthesize reusable magnetic porous microspheres (MPMS) of Fe₃O₄/poly(methylmethacrylate (MMA)-co-divinylbenzene (DVB)) is described in this paper. The magnetic microspheres were synthesized by suspension copolymerization. MMA was used as a monomer, DVB was used as a crosslinker, and the magnetic fluid was added to the organic phase. The morphology of MPMS was observed by scanning electron microscope (SEM) and other properties were tested by superconducting quantum interference device, Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), and nitrogen sorption-desorption techniques. The synthesized MPMS possessed a high specific surface area using toluene as a porogen. It was further found that the ratio of DVB to MMA, the ratio of porogen to monomer, and the type of porogen all affected the specific surface area and the morphology of the microspheres. Furthermore, the microspheres were applied to remove Rhodamine B from its aqueous solution. The results showed that the microspheres possessed good adsorption capacity for Rhodamine B. This result was due to the porous structure, polar groups, and superparamagnetic characteristic of the synthesized microspheres.

磁性多孔四氧化三铁/聚（甲基丙烯酸甲酯-co-二乙烯基苯）微球的制备、表征及其去除罗丹明B的应用研究

[1]Adnan, L.A., Yusoff, A.R.M., Hadibarata, T., et al., 2014. Biodegradation of bis-azo dye Reactive Black 5 by white-rot fungus Trametes gibbosa sp. WRF 3 and its metabolite characterization. Water, Air, & Soil Pollution, 225(10):1-11.

[2]Ahmed, M.A., Khafagy, R.M., Bishay, S.T., et al., 2013. Effective dye removal and water purification using the electric and magnetic Zn_0.5Co_0.5Al_0.5Fe_1.46La_0.04O₄/ polymer core-shell nanocomposites. Journal of Alloys and Compounds, 578:121-131.

[3]Almeida, E.J.R., Corso, C.R., 2014. Comparative study of toxicity of azo dye Procion Red MX-5B following biosorption and biodegradation treatments with the fungi Aspergillus niger and Aspergillus terreus. Chemosphere, 112:317-322.

[4]Chen, Y.H., Liu, Y.Y., Lin, R.H., et al., 2009. Photocatalytic degradation of p-phenylenediamine with TiO₂-coated magnetic PMMA microspheres in an aqueous solution. Journal of Hazardous Materials, 163(2-3):973-981.

[5]Cheng, Z., Zhang, L., Guo, X., et al., 2015. Adsorption behavior of Direct Red 80 and Congo Red onto activated carbon/surfactant: process optimization, kinetics and equilibrium. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 137:1126-1143.

[6]Crini, G., 2005. Recent developments in polysaccharide-based materials used as adsorbents in wastewater treatment. Progress in Polymer Science, 30(1):38-70.

[7]Debnath, S., Ballav, N., Nyoni, H., et al., 2015. Optimization and mechanism elucidation of the catalytic photo-degradation of the dyes Eosin Yellow (EY) and Naphthol blue black (NBB) by a polyaniline-coated titanium dioxide nanocomposite. Applied Catalysis B: Environmental, 163:330-342.

[8]Filice, S., D’Angelo, D., Libertino, S., et al., 2015. Graphene oxide and titania hybrid Nafion membranes for efficient removal of methyl orange dye from water. Carbon, 82:489-499.

[9]Fu, J., Chen, Z., Wang, M., et al., 2015. Adsorption of methylene blue by a high-efficiency adsorbent (polydopamine microspheres): kinetics, isotherm, thermodynamics and mechanism analysis. Chemical Engineering Journal, 259:53-61.

[10]Gao, H.J., Zhao, S.Y., Cheng, X.Y., et al., 2013. Removal of anionic azo dyes from aqueous solution using magnetic polymer multi-wall carbon nanotube nanocomposite as adsorbent. Chemical Engineering Journal, 223:84-90.

[11]Garrido-Ramirez, E.G., Theng, B.K.G., Mora, M.L., 2010. Clays and oxide minerals as catalysts and nanocatalysts in Fenton-like reactions-a review. Applied Clay Science, 47(3-4):182-192.

[12]Hameed, B.H., Din, A.T.M., Ahmad, A.L., 2007. Adsorption of methylene blue onto bamboo-based activated carbon: kinetics and equilibrium studies. Journal of Hazardous Materials, 141(3):819-825.

[13]Jarvis, K.L., Majewski, P., 2014. Removal of acid orange 7 dye from water via plasma-polymerized allylamine-coated quartz particles. Water, Air, and Soil Pollution, 225(12):2227.

[14]Khoobi, M., Delshad, T.M., Vosooghi, M., et al., 2015. Polyethyleneimine-modified superparamagnetic Fe₃O₄ nanoparticles: an efficient, reusable and water tolerance nanocatalyst. Journal of Magnetism and Magnetic Materials, 375:217-226.

[15]Li, D., Jiang, D., Chen, M., et al., 2010. An easy fabrication of monodisperse oleic acid-coated Fe₃O₄ nanoparticles. Materials Letters, 64(22):2462-2464.

[16]Liang, C.Z., Sun, S.P., Li, F.Y., et al., 2014. Treatment of highly concentrated wastewater containing multiple synthetic dyes by a combined process of coagulation/ flocculation and nanofiltration. Journal of Membrane Science, 469:306-315.

[17]Liu, Q., Wang, L., Xiao, A., et al., 2010. Templated preparation of porous magnetic microspheres and their application in removal of cationic dyes from wastewater. Journal of Hazardous Materials, 181(1-3):586-592.

[18]Luo, S., Duan, L., Sun, B., et al., 2015. Manganese oxide octahedral molecular sieve (OMS-2) as an effective catalyst for degradation of organic dyes in aqueous solutions in the presence of peroxymonosulfate. Applied Catalysis B: Environmental, 164:92-99.

[19]Macintyre, F.S., Sherrington, D.C., 2004. Control of porous morphology in suspension polymerized poly-(divinylbenzene) resins using oligomeric porogens. Macromolecules, 37(20):7628-7636.

[20]Mak, S.Y., Chen, D.H., 2004. Fast adsorption of methylene blue on polyacrylic acid-bound iron oxide magnetic nanoparticles. Dyes and Pigments, 61(1):93-98.

[21]Mao, J., Jiang, W., Gu, J., et al., 2014. Synthesis of P (St-DVB)/Fe₃O₄ microspheres and application for oil removal in aqueous environment. Applied Surface Science, 317:787-793.

[22]Meshko, V., Markovska, L., Mincheva, M., et al., 2001. Adsorption of basic dyes on granular acivated carbon and natural zeolite. Water Research, 35(14):3357-3366.

[23]Mu, B., Wang, A., 2015. One-pot fabrication of multifunctional superparamagnetic attapulgite/Fe₃O₄/ polyaniline nanocomposites served as an adsorbent and catalyst support. Journal of Materials Chemistry A, 3(1):281-289.

[24]Namasivayam, C., Kavitha, D., 2002. Removal of Congo Red from water by adsorption onto activated carbon prepared from coir pith, an agricultural solid waste. Dyes and Pigments, 54(1):47-58.

[25]Ning, Y.C., 2000. Structural Identification of Organic Compounds and Organic Spectroscopy. Science Press, Beijing, China (in Chinese).

[26]Palma-Goyes, R.E., Silva-Agredo, J., Gonzalez, I., et al., 2014. Comparative degradation of indigo carmine by electrochemical oxidation and advanced oxidation processes. Electrochimica Acta, 140:427-433.

[27]Rabelo, D., Coutinho, F.M.B., 1993. Cosolvency effects of benzyl alcohol and heptane on the formation of macroporous styrene-divinylbenzene copolymers. Polymer Bulletin, 31(5):585-592.

[28]Svata, M., 1972. Determination of pore size and shape distribution from porosymmetric hysteresis curves. Powder Technology, 5(6):345-349.

[29]Tai, Y.L., Wang, L., Gao, J.M., et al., 2011. Synthesis of Fe₃O₄@poly(methylmethacrylate-co-divinylbenzene) magnetic porous microspheres and their application in the separation of phenol from aqueous solutions. Journal of Colloid and Interface Science, 360(2):731-738.

[30]Tang, M., Zhang, S., Li, X., et al., 2014. Fabrication of magnetically recyclable Fe₃O₄@Cu nanocomposites with high catalytic performance for the reduction of organic dyes and 4-nitrophenol. Materials Chemistry and Physics, 148(3):639-647.

[31]Tang, Q., Lin, J., Wu, Z., et al., 2007. Preparation and photocatalytic degradability of TiO₂/polyacrylamide composite. European Polymer Journal, 43(6):2214-2220.

[32]Vimonses, V., Lei, S., Jin, B., et al., 2009. Kinetic study and equilibrium isotherm analysis of Congo Red adsorption by clay materials. Chemical Engineering Journal, 148(2-3):354-364.

[33]Wang, M., Cui, S., Yang, X., et al., 2015. Synthesis of g-C₃N₄/Fe₃O₄ nanocomposites and application as a new sorbent for solid phase extraction of polycyclic aromatic hydrocarbons in water samples. Talanta, 132:922-928.

[34]Wang, S.B., Li, H., Xu, L.Y., 2006. Application of zeolite MCM-22 for basic dye removal from wastewater. Journal of Colloid and Interface Science, 295(1):71-78.

[35]Yan, T.G., Wang, L.J., 2014. Adsorption of C.I. Reactive Red 228 and Congo Red dye from aqueous solution by amino-functionalized Fe₃O₄ particles: kinetics, equilibrium, and thermodynamics. Water Science & Technology, 69(3):612-621.

[36]Zhao, S., Gao, B., Yue, Q., et al., 2014. Effect of Enteromorpha polysaccharides on coagulation performance and kinetics for dye removal. Colloids and Surfaces A: Physico-chemical and Engineering Aspects, 456:253-260.

[37]Zolgharnein, J., Bagtash, M., Shariatmanesh, T., 2015. Simultaneous removal of binary mixture of Brilliant Green and Crystal Violet using derivative spectrophoto-metric determination, multivariate optimization and adsorption characterization of dyes on surfactant modified nano-gamma-alumina. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 137: 1016-1028.