Functional graphene oxide nanosheets modified with cyclodextrins for removal of Bisphenol A from water

doi:10.1016/j.cjche.2021.02.018

Abstract

Abstract: A novel type of functional graphene oxide nanosheets (GNs) modified with β-cyclodextrins (β-CDs) have been developed by coating dopamine-functionalized cyclodextrin (DACD) molecules on GNs for removing Bisphenol A (BPA) molecules from water. The DACD molecules with both β-CD groups for achieving adsorption property and dopamine (DA) groups for achieving adhesion property are synthesized by grafting DA onto carboxymethyl-β-cyclodextrin (CmβCD). The proposed DACD molecules can be firmly coated on the surfaces of various inorganic and organic substrates. Due to the large specific surface area of GNs, DACD-coated GNs (DACD@GNs) are proposed for efficient adsorption separation of BPA molecules from water. Due to the host-gust complexation between the BPA molecules in water and β-CDs on DACD@GNs, the fabricated DACD@GNs exhibit excellent adsorption performances. The adsorption kinetics can be explained via the pseudo-second-order model effectively. The experimental adsorption capacity of DACD@GNs is 11.29 mg·g^-1 for BPA. Furthermore, after the adsorption process, the DACD@GNs can be easily separated from aqueous solutions via vacuum filtration with porous membranes, and then regenerated by simply washing with ethanol. The proposed strategy in this study can be used for effectively functionalizing the surfaces of various substrates with functional β-CDs, which is highly promising in applications in the field of adsorption separations, especially water treatments.

Key words: Adsorption separation, β-Cyclodextrin, Bisphenol A, Graphene oxide nanosheets, Dopamine

摘要： A novel type of functional graphene oxide nanosheets (GNs) modified with β-cyclodextrins (β-CDs) have been developed by coating dopamine-functionalized cyclodextrin (DACD) molecules on GNs for removing Bisphenol A (BPA) molecules from water. The DACD molecules with both β-CD groups for achieving adsorption property and dopamine (DA) groups for achieving adhesion property are synthesized by grafting DA onto carboxymethyl-β-cyclodextrin (CmβCD). The proposed DACD molecules can be firmly coated on the surfaces of various inorganic and organic substrates. Due to the large specific surface area of GNs, DACD-coated GNs (DACD@GNs) are proposed for efficient adsorption separation of BPA molecules from water. Due to the host-gust complexation between the BPA molecules in water and β-CDs on DACD@GNs, the fabricated DACD@GNs exhibit excellent adsorption performances. The adsorption kinetics can be explained via the pseudo-second-order model effectively. The experimental adsorption capacity of DACD@GNs is 11.29 mg·g^-1 for BPA. Furthermore, after the adsorption process, the DACD@GNs can be easily separated from aqueous solutions via vacuum filtration with porous membranes, and then regenerated by simply washing with ethanol. The proposed strategy in this study can be used for effectively functionalizing the surfaces of various substrates with functional β-CDs, which is highly promising in applications in the field of adsorption separations, especially water treatments.

关键词: Adsorption separation, β-Cyclodextrin, Bisphenol A, Graphene oxide nanosheets, Dopamine

Zhi-Hao Chen, Zhuang Liu, Lei Zhang, Quan-Wei Cai, Jia-Qi Hu, Wei Wang, Xiao-Jie Ju, Rui Xie, Liang-Yin Chu. Functional graphene oxide nanosheets modified with cyclodextrins for removal of Bisphenol A from water[J]. Chinese Journal of Chemical Engineering, 2021, 39(11): 79-87.

References

[1] A. Alsbaiee, B.J. Smith, L.L. Xiao, Y.H. Ling, D.E. Helbling, W.R. Dichtel, Rapid removal of organic micropollutants from water by a porous b-cyclodextrin polymer, Nature 529(7585) (2016) 190-194.
[2] H. Wang, Y.G. Liu, G.M. Zeng, X.J. Hu, X. Hu, T.T. Li, H.Y. Li, Y.Q. Wang, L.H. Jiang, Grafting of b-cyclodextrin to magnetic graphene oxide via ethylenediamine and application for Cr(VI) removal, Carbohydr. Polym. 113(2014) 166-173.
[3] G. Crini, Studies on adsorption of dyes on beta-cyclodextrin polymer, Bioresour. Technol. 90(2) (2003) 193-198.
[4] G.Z. Kyzas, N.K. Lazaridis, D.N. Bikiaris, Optimization of chitosan and bcyclodextrin molecularly imprinted polymer synthesis for dye adsorption, Carbohydr. Polym. 91(1) (2013) 198-208.
[5] E.Y. Ozmen, M. Sezgin, A. Yilmaz, M. Yilmaz, Synthesis of beta-cyclodextrin and starch based polymers for sorption of azo dyes from aqueous solutions, Bioresour. Technol. 99(3) (2008) 526-531.
[6] L.P. Zhang, Z. Liu, Y. Faraj, Y. Zhao, R. Zhuang, R. Xie, X.J. Ju, W. Wang, L.Y. Chu, High-flux efficient catalytic membranes incorporated with iron-based Fentonlike catalysts for degradation of organic pollutants, J. Membr. Sci. 573(2019) 493-503.
[7] M. Younes, H. Galal-Gorchev, Pesticides in drinking water:A case study, Food Chem. Toxicol. 38(1 Suppl) (2000) S87-S90.
[8] E.D. Ongley, Control of Water Pollution from Agriculture, Food and Agriculture Organization of the United Nation, Rome (1996) 53.
[9] R.P. Schwarzenbach, B.I. Escher, K. Fenner, T.B. Hofstetter, C.A. Johnson, U. von Gunten, B. Wehrli, The challenge of micropollutants in aquatic systems, Science 313(5790) (2006) 1072-1077.
[10] S.D. Richardson, T.A. Ternes, Water analysis:emerging contaminants and current issues, Anal. Chem. 86(6) (2014) 2813-2848.
[11] K.E. Murray, S.M. Thomas, A.A. Bodour, Prioritizing research for trace pollutants and emerging contaminants in the freshwater environment, Environ. Pollut. 158(12) (2010) 3462-3471.
[12] R. McKinlay, J.A. Plant, J.N. Bell, N. Voulvoulis, Endocrine disrupting pesticides:implications for risk assessment, Environ. Int. 34(2) (2008) 168-183.
[13] R.P. Schwarzenbach, T. Egli, T.B. Hofstetter, U. von Gunten, B. Wehrli, Global water pollution and human health, Annu. Rev. Environ. Resour. 35(1) (2010) 109-136.
[14] P. Lo Meo, G. Lazzara, L. Liotta, S. Riela, R. Noto, Cyclodextrin-calixarene copolymers as a new class of nanosponges, Polym. Chem. 5(15) (2014) 4499- 4510.
[15] G. Crini, M. Morcellet, Synthesis and applications of adsorbents containing cyclodextrins, J. Sep. Sci. 25(13) (2002) 789-813.
[16] H.L. Zheng, Y. Gao, K.R. Zhu, Q. Wang, M. Wakeel, A. Wahid, N.S. Alharbi, C.L. Chen, Investigation of the adsorption mechanisms of Pb(II) and 1-naphthol by β-cyclodextrin modified graphene oxide nanosheets from aqueous solution, J. Colloid Interface Sci. 530(2018) 154-162.
[17] S.S. Wang, Y. Li, X.B. Fan, F.B. Zhang, G.L. Zhang, Β-cyclodextrin functionalized graphene oxide:An efficient and recyclable adsorbent for the removal of dye pollutants, Front. Chem. Sci. Eng. 9(1) (2015) 77-83.
[18] M. Lv, X.B. Wang, J. Li, X.Y. Yang, C.A. Zhang, J. Yang, H. Hu, Cyclodextrinreduced graphene oxide hybrid nanosheets for the simultaneous determination of lead(II) and cadmium(II) using square wave anodic stripping voltammetry, Electrochim. Acta 108(2013) 412-420.
[19] G.C. Wei, R.H. Dong, D. Wang, L. Feng, S.L. Dong, A.X. Song, J.C. Hao, Functional materials from the covalent modification of reduced graphene oxide and bcyclodextrin as a drug delivery carrier, New J. Chem. 38(1) (2014) 140-145.
[20] Y.J. Guo, S.J. Guo, J.T. Ren, Y.M. Zhai, S.J. Dong, E.K. Wang, Cyclodextrin functionalized graphene nanosheets with high supramolecular recognition capability:Synthesis and host-guest inclusion for enhanced electrochemical performance, ACS Nano 4(7) (2010) 4001-4010.
[21] M.S. Samuel, E. Selvarajan, K. Subramaniam, T. Mathimani, S. Seethappan, A. Pugazhendhi, Synthesized b-cyclodextrin modified graphene oxide (b-CD-GO) composite for adsorption of cadmium and their toxicity profile in cervical cancer (HeLa) cell lines, Process. Biochem. 93(2020) 28-35.
[22] F.P. Zhan, F. Gao, X. Wang, L.Q. Xie, F. Gao, Q.X. Wang, Determination of lead(II) by adsorptive stripping voltammetry using a glassy carbon electrode modified with b-cyclodextrin and chemically reduced graphene oxide composite, Microchim. Acta 183(3) (2016) 1169-1176.
[23] F. Chekin, V. Mishyn, A. Barras, J. Lyskawa, R. Ye, S. Melinte, P. Woisel, R. Boukherroub, S. Szunerits, Dopamine-functionalized cyclodextrins:modification of reduced graphene oxide based electrodes and sensing of folic acid in human serum, Anal. Bioanal. Chem. 411(20) (2019) 5149-5157.
[24] Z. Liu, F. Luo, X.J. Ju, R. Xie, Y.M. Sun, W. Wang, L.Y. Chu, Gating membranes for water treatment:Detection and removal of trace Pb²⁺ ions based on molecular recognition and polymer phase transition, J. Mater. Chem. A 1(34) (2013) 9659.
[25] W.S. Hummers, E. Richard, Offerman, preparation of graphitic oxide, J. Am. Chem. Soc. 80(1957) 1339-1440.
[26] C. Bielawski, D. Dreyer, S. Park, R. Ruoff, The chemistry of grapheme oxide, Chem. Soc. Rev. 39(2010) 228-240.