Abstract
Copper in drinking water causes a significant environmental problem. Composite material based on alginate hydrogel has been gaining attention in the field of Cu(II) adsorption. However, alginate-based hydrogel exhibits poor mechanical property and relative low adsorption capacity which limit their application. The present study is devoted to the modification of chitosan/calcium alginate/Fe3O4 (CAF) hydrogel microsphere by NaOH solution for enhancement of Cu(II) adsorption. Results reveal that modification of CAF via NaOH solution significantly improves the mechanical strength and Cu2+ adsorption capacity of pristine materials. FTIR and XRD analysis confirms that CAF and newly prepared materials (NACAF) are successfully prepared. SEM and EDX are employed to analyze the surface morphology and elemental composition, respectively, both before and after their loading with Cu2+. XPS study demonstrates adsorption mechanism is based on chelation and ion-exchange. Compressive stress-strain curves demonstrate NACAF has better mechanical performance than CAF. The adsorption kinetics of the two adsorbents follow a pseudo-second-order model. The equilibrium data were best described by Langmuir isotherm model, and the estimated maximum equilibrium sorption capacity, q m,is 261.31 mg/g for the NACAF, which is larger than that of CAF (145.39 mg/g). Hence, NACAF shows excellent mechanical strength and high sorption capacity for Cu2+. It has great potential for Cu(II) removal in aqueous solutions.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Algothmi WM, Bandaru NM, Yu Y, Shapter JG, Ellis AV (2013) Alginate-graphene oxide hybrid gel beads: an efficient copper adsorbent material. J Colloid Interface Sci 397:32–38. https://doi.org/10.1016/j.jcis.2013.01.051
Alves Gurgel LV, de Freitas RP, Gil LF (2008) Adsorption of Cu (II), Cd (II), and Pb (II) from aqueous single metal solutions by sugarcane bagasse and mercerized sugarcane bagasse chemically modified with succinic anhydride. Carbohydr Polym 74(4):922–929. https://doi.org/10.1016/j.carbpol.2008.05.023
Bang S, Choi J-W, Cho K, Chung C, Kang H, Hong SW (2016) Simultaneous reduction of copper and toxicity in semiconductor wastewater using protonated alginate beads. Chem Eng J 288:525–531. https://doi.org/10.1016/j.cej.2015.12.025
Bayramoglu G, Arica MY (2016) MCM-41 silica particles grafted with polyacrylonitrile: modification in to amidoxime and carboxyl groups for enhanced uranium removal from aqueous medium. Microporous Mesoporous Mater 226:117–124. https://doi.org/10.1016/j.micromeso.2015.12.040
Boamah PO, Huang Y, Hua M, Onumah J, Sam-Amoah LK, Boamah PO, Qian Y, Zhang Q (2016) Sorption of copper onto low molecular weight chitosan derivative from aqueous solution. Ecotoxicol Environ Saf 129:154–163. https://doi.org/10.1016/j.ecoenv.2016.01.014
Caprioli F, Marrani AG, Di Castro V (2014) Tuning the composition of aromatic binary self-assembled monolayers on copper: an XPS study. Appl Surf Sci 303:30–36. https://doi.org/10.1016/j.apsusc.2014.02.035
Ceglowski M, Schroeder G (2015) Removal of heavy metal ions with the use of chelating polymers obtained by grafting pyridine-pyrazole ligands onto polymethylhydrosiloxane. Chem Eng J 259:885–893. https://doi.org/10.1016/j.cej.2014.08.058
Deng S, Bai RB (2003) Aminated polyacrylonitrile fibers for humic acid adsorption: behaviors and mechanisms. Environ Sci Technol 37(24):5799–5805. https://doi.org/10.1021/es034399d
Donia AM, Atia AA, Moussa EMM, El-Sherif AM, El-Magied MOA (2009) Removal of uranium (VI) from aqueous solutions using glycidyl methacrylate chelating resins. Hydrometallurgy 95(3-4):183–189. https://doi.org/10.1016/j.hydromet.2008.05.037
Dragan ES, Loghin DFA, Cocarta AI (2014) Efficient sorption of Cu2+ by composite chelating sorbents based on potato starch-graft-polyamidoxime embedded in chitosan beads. ACS Appl Mater Interfaces 6(19):16577–16592. https://doi.org/10.1021/am504480q
Duan P, Yan C, Zhou W, Ren D (2016) Development of fly ash and iron ore tailing based porous geopolymer for removal of Cu (II) from wastewater. Ceram Int 42(12):13507–13518. https://doi.org/10.1016/j.ceramint.2016.05.143
Edwards-Levy F, Levy MC (1999) Serum albumin-alginate coated beads: mechanical properties and stability. Biomaterials 20(21):2069–2084. https://doi.org/10.1016/S0142-9612(99)00111-8
Huang Y, Wang Z (2017) Preparation of composite aerogels based on sodium alginate, and its application in removal of Pb2+and Cu2+from water. Int J Biol Macromol
Imamoglu M, Tekir O (2008) Removal of copper (II) and lead (II) ions from aqueous solutions by adsorption on activated carbon from a new precursor hazelnut husks. Desalination 228(1-3):108–113. https://doi.org/10.1016/j.desal.2007.08.011
Jin L, Bai RB (2002) Mechanisms of lead adsorption on chitosan/PVA hydrogel beads. Langmuir 18(25):9765–9770. https://doi.org/10.1021/la025917l
Karthik R, Meenakshi S (2015) Removal of Cr (VI) ions by adsorption onto sodium alginate-polyaniline nanofibers. Int J Biol Macromol 72:711–717. https://doi.org/10.1016/j.ijbiomac.2014.09.023
Kong X-P, Wang J (2016) Copper (II) adsorption on the kaolinite(001) surface: insights from first-principles calculations and molecular dynamics simulations. Appl Surf Sci 389:316–323. https://doi.org/10.1016/j.apsusc.2016.07.112
Lakouraj MM, Mojerlou F, Zare EN (2014) Nanogel and superparamagnetic nanocomposite based on sodium alginate for sorption of heavy metal ions. Carbohydr Polym 106:34–41. https://doi.org/10.1016/j.carbpol.2014.01.092
Liao B, W-y S, Guo N, S-l D, S-j S (2016) Comparison of Co2+ adsorption by chitosan and its triethylene-tetramine derivative: performance and mechanism. Carbohydr Polym 151:20–28. https://doi.org/10.1016/j.carbpol.2016.05.053
Liu C, Bai R, Hong L (2006) Diethylenetriamine-grafted poly(glycidyl methacrylate) adsorbent for effective copper ion adsorption. J Colloid Interface Sci 303(1):99–108. https://doi.org/10.1016/j.jcis.2006.07.057
Liu H, Kong D, Sun W, Li Q, Zhou Z, Ren Z (2016) Effect of anions on the polymerization and adsorption processes of Cu(II) ion-imprinted polymers. Chem Eng J 303:348–358. https://doi.org/10.1016/j.cej.2016.06.004
Lopes CMA, Felisberti MI (2003) Mechanical behaviour and biocompatibility of poly(1-vinyl-2-pyrrolidinone)-gelatin IPN hydrogels. Biomaterials 24(7):1279–1284. https://doi.org/10.1016/S0142-9612(02)00448-9
Mittal A, Ahmad R, Hasan I (2016) Biosorption of Pb2+, Ni2+ and Cu2+ ions from aqueous solutions by L-cystein-modified montmorillonite-immobilized alginate nanocomposite. Desalin Water Treat 57(38):17790–17807. https://doi.org/10.1080/19443994.2015.1086900
Monier M, Ayad DM, Sarhan AA (2010a) Adsorption of Cu (II), Hg (II), and Ni (II) ions by modified natural wool chelating fibers. J Hazard Mater 176(1-3):348–355. https://doi.org/10.1016/j.jhazmat.2009.11.034
Monier M, Ayad DM, Wei Y, Sarhan AA (2010b) Adsorption of Cu (II), Co (II), and Ni (II) ions by modified magnetic chitosan chelating resin. J Hazard Mater 177(1-3):962–970. https://doi.org/10.1016/j.jhazmat.2010.01.012
Ngah WSW, Endud CS, Mayanar R (2002) Removal of copper (II) ions from aqueous solution onto chitosan and cross-linked chitosan beads. React Funct Polym 50(2):181–190. https://doi.org/10.1016/S1381-5148(01)00113-4
Ngah WSW, Fatinathan S (2008) Adsorption of Cu (II) ions in aqueous solution using chitosan beads, chitosan-GLA beads and chitosan-alginate beads. Chem Eng J 143(1-3):62–72. https://doi.org/10.1016/j.cej.2007.12.006
Ngah WSW, Teong LC, Hanafiah MAKM (2011) Adsorption of dyes and heavy metal ions by chitosan composites: a review. Carbohydr Polym 83(4):1446–1456. https://doi.org/10.1016/j.carbpol.2010.11.004
Niu Y, Ying D, Li K, Wang Y, Jia J (2016) Fast removal of copper ions from aqueous solution using an eco-friendly fibrous adsorbent. Chemosphere 161:501–509. https://doi.org/10.1016/j.chemosphere.2016.07.017
Pang Y, Zeng G, Tang L, Zhang Y, Liu Y, Lei X, Li Z, Zhang J, Liu Z, Xiong Y (2011) Preparation and application of stability enhanced magnetic nanoparticles for rapid removal of Cr (VI). Chem Eng J 175:222–227. https://doi.org/10.1016/j.cej.2011.09.098
Peppas NA, Hilt JZ, Khademhosseini A, Langer R (2006) Hydrogels in biology and medicine: from molecular principles to bionanotechnology. Adv Mater 18(11):1345–1360. https://doi.org/10.1002/adma.200501612
Philippova O, Barabanova A, Molchanov V, Khokhlov A (2011) Magnetic polymer beads: recent trends and developments in synthetic design and applications. Eur Polym J 47(4):542–559. https://doi.org/10.1016/j.eurpolymj.2010.11.006
Ren Y, Abbood HA, He F, Peng H, Huang K (2013) Magnetic EDTA-modified chitosan/SiO2/Fe3O4 adsorbent: preparation, characterization, and application in heavy metal adsorption. Chem Eng J 226:300–311. https://doi.org/10.1016/j.cej.2013.04.059
Shao L, Wang X, Ren Y, Wang S, Zhong J, Chu M, Tang H, Luo L, Xie D (2016) Facile fabrication of magnetic cucurbit 6 uril/graphene oxide composite and application for uranium removal. Chem Eng J 286:311–319. https://doi.org/10.1016/j.cej.2015.10.062
Sheng G, Yang P, Tang Y, Hu Q, Li H, Ren X, Hu B, Wang X, Huang Y (2016) New insights into the primary roles of diatomite in the enhanced sequestration of UO2 2+ by zerovalent iron nanoparticles: an advanced approach utilizing XPS and EXAFS. Appl Catal B Environ 193:189–197. https://doi.org/10.1016/j.apcatb.2016.04.035
Smitha B, Sridhar S, Khan AA (2005) Chitosan-sodium alginate polyion complexes as fuel cell membranes. Eur Polym J 41(8):1859–1866. https://doi.org/10.1016/j.eurpolymj.2005.02.018
Tamez C, Hernandez R, Parsons JG (2016) Removal of Cu (II) and Pb (II) from aqueous solution using engineered iron oxide nanoparticles. Microchem J 125:97–104. https://doi.org/10.1016/j.microc.2015.10.028
Vani TJS, Reddy NS, Reddy PR, Rao K, Ramkumar J, Reddy AVR (2014) Synthesis, characterization, and metal uptake capacity of a new polyaniline and poly(acrylic acid) grafted sodium alginate/gelatin adsorbent. Desalin Water Treat 52(1-3):526–535. https://doi.org/10.1080/19443994.2013.846460
Wang J-s, R-t P, Yang J-h, Y-c L, Hu X-j (2011) Preparation of ethylenediamine-modified magnetic chitosan complex for adsorption of uranyl ions. Carbohydr Polym 84(3):1169–1175. https://doi.org/10.1016/j.carbpol.2011.01.007
Wang L, Yuan L, Chen K, Zhang Y, Deng Q, Du S, Huang Q, Zheng L, Zhang J, Chai Z, Barsoum MW, Wang X, Shi W (2016) Loading actinides in multilayered structures for nuclear waste treatment: the first case study of uranium capture with vanadium carbide MXene. ACS Appl Mater Interfaces 8(25):16396–16403. https://doi.org/10.1021/acsami.6b02989
Wang W, Kang Y, Wang A (2013) One-step fabrication in aqueous solution of a granular alginate-based hydrogel for fast and efficient removal of heavy metal ions. J Polym Res 20(3) doi: https://doi.org/10.1007/s10965-013-0101-0
Wu N, Li Z (2013) Synthesis and characterization of poly(HEA/MALA) hydrogel and its application in removal of heavy metal ions from water. Chem Eng J 215:894–902
Yavuz O, Altunkaynak Y, Guzel F (2003) Removal of copper, nickel, cobalt and manganese from aqueous solution by kaolinite. Water Res 37(4):948–952. https://doi.org/10.1016/S0043-1354(02)00409-8
Yi X, He J, Guo Y, Han Z, Yang M, Jin J, Gu J, Ou M, Xu X (2017a) Encapsulating Fe3O4 into calcium alginate coated chitosan hydrochloride hydrogel beads for removal of Cu (II) and U (VI) from aqueous solutions. Ecotoxicol Environ Saf 147:699–707
Yi X, Xu Z, Liu Y, Guo X, Ou M, Xu X (2017b) Highly efficient removal of uranium (VI) from wastewater by polyacrylic acid hydrogels. RSC Adv 7(11):6278–6287. https://doi.org/10.1039/C6RA26846C
Zhang H, Yong X, Zhou J, Deng J, Wu Y (2016) Biomass vanillin-derived polymeric microspheres containing functional aldehyde groups: preparation, characterization, and application as adsorbent. ACS Appl Mater Interfaces 8(4):2753–2763. https://doi.org/10.1021/acsami.5b11042
Zhao J, Liu J, Li N, Wang W, Nan J, Zhao Z, Cui F (2016) Highly efficient removal of bivalent heavy metals from aqueous systems by magnetic porous Fe3O4-MnO2: adsorption behavior and process study. Chem Eng J 304:737–746. https://doi.org/10.1016/j.cej.2016.07.003
Author information
Authors and Affiliations
Corresponding authors
Additional information
Responsible editor: Guilherme L. Dotto
Rights and permissions
About this article
Cite this article
Yi, X., Yang, M., Mo, L. et al. Modification of chitosan/calcium alginate/Fe3O4 hydrogel microsphere for enhancement of Cu(II) adsorption. Environ Sci Pollut Res 25, 3922–3932 (2018). https://doi.org/10.1007/s11356-017-0802-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-017-0802-8