Novel Amphoteric Cryogels for Cd²⁺ Ions Removal from Aqueous Solutions

Abstract:

In this work, amphoteric cryogels based on N,N-dimethyl acrylamide, methacrylic acid and allylamine, crosslinked by N,N-methylenebisacrylamide were synthesized by free-radical polymerization in cryo-conditions. The synthesized cryogels were used for the removal of cadmium ions from aqueous solutions under different pH values. The chemical structure was studied by FTIR, porosity by nitrogen adsorption and morphology by scanning electron microscopy and texture analyzer. The amphoteric properties of cryogels were studied by zeta potential measurements. Adsorption tests revealed that cryogels exhibit 3 times higher adsorption capacity at pH 6.0 than at pH 4.0. The maximum adsorption capacity of the amphoteric cryogels for Cd²⁺ was 113 mg/g, at pH 6.0 and initial Cd²⁺ concentration 100 ppm. The results suggest that the predominant removal mechanism is ion exchange between sodium, which initially presents in the structure of the cryogel, and cadmium from the aqueous phase. Recovery studies suggested that the cryogels used can be regenerated and efficiently reused.

• Periodical: Key Engineering Materials (Volume 775)
• Pages: 376-382
• DOI: https://doi.org/10.4028/www.scientific.net/KEM.775.376
• Online since: August 2018
• Authors: Alzhan Baimenov, Dmitriy Berillo, Leila Abylgazina, Stavros G. Poulopoulos, Vassilis J. Inglezakis*
• Keywords: Adsorption, Cadmium Removal, Cryogel, Ion-Exchange

References

[1] Vodela JK, Renden JA, Lenz SD, Henney WHM, Kemppainen BW. Drinking water contaminants (Arsenic, cadmium, lead, benzene, and trichloroethylene) 1. Interaction of contaminants with nutritional status on general performance and immune function in broiler chickens. Pollution Science. 76 (1997).

DOI: 10.1093/ps/76.11.1474

[2] Öztürk M, Özözen G, Minareci O, Minareci E. Determination of heavy metals in fish, water and sediments of Avsar Dam Lake in Turkey. Iran J Environ Health Sci Eng. 6 (2009) 73–80.

[3] Bhattacharyya MH, Wilson AK, Rajan SS, Jonah M (2000) Biochemical pathways in cadmium toxicity. In: Zalups RK, Koropatnick J (Eds), Molecular biology and toxicology of metals, Taylor and Francis, London, p.34–74.

[4] H. Abu Qdaisa, H. Moussab, Removal of heavy metals from wastewater by membrane processes: a comparative study, Desalination. 164 (2004), 105-110.

DOI: 10.1016/s0011-9164(04)00169-9

[5] S. Babel, T.A. Kurniawan Cr(VI) removal from synthetic wastewater using coconut shell charcoal and commercial activated carbon modified with oxidizing agents and/or chitosan, Chemospher., 54 (7) (2004), 951-967.

DOI: 10.1016/j.chemosphere.2003.10.001

[6] C. Bloocher, J. Dorda, V. Mavrov, H. Chmiel, N.K. Lazaridis, K.A. Matis, Hybrid flotation-membrane filtration process for the removal of heavy metal ions from wastewater, Water Res., 37 (2003), 4018-4027.

DOI: 10.1016/s0043-1354(03)00314-2

[7] H.A. Essawy, H.S. Ibrahim, Synthesis and characterization of poly(vinylpyrrolidone-co- methylacrylate) hydrogel for removal and recovery of heavy metal ions from wastewater. React. Funct. Polym., 61 (2004), 421-432.

DOI: 10.1016/j.reactfunctpolym.2004.08.003

[8] D. Fenga, C. Aldrich, Adsorption of heavy metals by biomaterials derived from the marine alga Ecklonia maxima. Hydrometallurgy, 73 (2004), 1-10.

DOI: 10.1016/s0304-386x(03)00138-5

[9] V.K. Gupta, C.K. Jain, I. Ali, M. Sharma, S.K. Saini, Removal of cadmium and nickel from wastewater using bagasse fly ash – a sugar industry waste.Water Res., 37 (2003), 4038-4044.

DOI: 10.1016/s0043-1354(03)00292-6

[10] J. Lv, K.Y. Wang, T.S. Chung, Investigation of amphoteric polybenzimidazole (PBI) nanofiltration hollow fiber membrane for both cation and anions removal. J. Membr. Sci., 310 (2008), 557-566.

DOI: 10.1016/j.memsci.2007.11.050

[11] V.M. Gun'ko, I.N. Savina, S.V. Mikhalovsky, Cryogels: Morphological, structural and adsorption characterization. Advances in Colloid and Interface Science, 187–188 (2013), 1-46.

DOI: 10.1016/j.cis.2012.11.001

[12] L. Onnby , C. Giorgi , F.M. Plieva, B. Mattiasson, Removal of heavy metals from water effluents using supermacroporous metal chelating cryogels. Biotechnol Prog. 26(5) (2010) 1295-1302.

DOI: 10.1002/btpr.422

[13] V.I Lozinsky, Cryogels on the basis of natural and synthetic polymers: preparation, properties and application Russian Chemical Reviews,71(6) (2002), 489.

DOI: 10.1070/rc2002v071n06abeh000720

[14] D. Ceylan, M. M. Ozmen, and O. Okay, Swelling–deswelling kinetics of ionic poly(acrylamide) hydrogels and cryogels. J. Appl. Polym. Sci., 99 (2006) 319-325.

DOI: 10.1002/app.22023

[15] S. Gorgieva, V. Kokol Processing of gelatin-based cryogels with improved thermomechanical resistance, pore size gradient, and high potential for sustainable protein drug release March Journal of Biomedical Materials Research Part A 103(3) (2015).

DOI: 10.1002/jbm.a.35261

[16] Kirsebom, Harald, et al. Enzyme‐Catalyzed Crosslinking in a Partly Frozen State: A New Way to Produce Supermacroporous Protein Structures., Macromolecular bioscience 13.1 (2013): 67-76.

DOI: 10.1002/mabi.201200343

[17] Doretti L.,Ferrara D., gattoline P., Lora S., Schiavon F., and Veronese F.M. (1998). PEG-modified glucose oxidase immobilized on a PVA cruogel membrane for amperometric biosensor applications. Talanta 45(5): 891-898.

DOI: 10.1016/s0039-9140(97)00191-4

[18] D. Berillo, B. Mattiasson, and H. Kirsebom, Cryogelation of chitosan using noble-metal ions: in situ formation of nanoparticles. Biomacromolecules 15(6) (2014) 2246-2255.

DOI: 10.1021/bm5003834

[19] O. Zaushitsyna, , et al. Cryostructured and crosslinked viable cells forming monoliths suitable for bioreactor applications. Topics in Catalysis 57(5) (2014) 339-348.

DOI: 10.1007/s11244-013-0189-9

[20] D. Çimen, D. Türkmen and A. Denizli, Poly-L-Histidine Attached Poly(glycidyl methacrylate) Cryogels for Heavy Metal Removal. Journal of Macromolecular Science, Part A, 52:9 (2015), 724-731.

DOI: 10.1080/10601325.2015.1063868

[21] N. Sahiner, S. Demirci, M. Sahiner, S. Yilmaz,H. Al-Lohedan, The use of superporous p(3-acrylamidopropyl)trimethyl ammonium chloride cryogels for removal of toxic arsenate anions. Journal of Environmental Management 152 (2015) 66-74.

DOI: 10.1016/j.jenvman.2015.01.023

[22] L. Önnby, H. Kirsebom, Cryogel-supported titanate nanotubes for waste treatment: Impact on methane production and bio-fertilizer quality. Journal of Biotechnology 207 (2015) 58-66.

DOI: 10.1016/j.jbiotec.2015.05.014

[23] L. Doretti, D. Ferrara, S. Lora, F. Schiavon and F.M. Veronese, Acetylcholine biosensor involving entrapment of acetylcholinesterase and poly (ethylene glycole)-modified chilone oxidase in a poly (vinyl alcohol) cryogel membrane. Enzyme and Microbial Technology 27(3) (2000).

DOI: 10.1016/s0141-0229(00)00210-6

[24] M. Kurozumi, Y. Yano, S. Kiyoyama, A. Kumar and K. Shiomori, Adsorption properties of arsenic(v) by polyacrylamide cryogel containing iron hydroxide oxide particles prepared by in situ method. Resources Processing 62 (2015) 17–23.

DOI: 10.4144/rpsj.62.17

[25] S. Abdurrahmanoglu, V. Can, O. Okay, Equilibrium swelling behavior and elastic properties of polymer-clay nanocomposite hydrogels.  J. Appl. Polym. Sci. 109 (2008) 3714-3724.

DOI: 10.1002/app.28607