Hyperbranched magnetic polymer: highly efficient removal of Cr(VI) and application in electroplating wastewater

doi:10.1007/s11705-023-2303-2

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (10) : 1568-1580 https://doi.org/10.1007/s11705-023-2303-2

RESEARCH ARTICLE

Hyperbranched magnetic polymer: highly efficient removal of Cr(VI) and application in electroplating wastewater

Nan Sun, Qing Wu, Lifang Jin, Zichen Zhu, Jianhui Sun(

), Shuying Dong, Haijiao Xie, Chunyan Zhang, Yanrui Cui

Key Laboratory for Yellow River and Huai River Water Environmental and Pollution Control, Ministry of Education, and Henan Key Laboratory for Environmental Pollution Control, School of Environment, Henan Normal University, Xinxiang 453007, China

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Abstract

By using a two-step hydrothermal method and trithiocyanuric acid (TTCA), 2,4,6-trihydrazino-1,3,5-triazine (THT), and Fe₃O₄ as raw materials, a spherical magnetic adsorbent polymer (TTCA/THT@Fe₃O₄) was synthesized to achieve the efficient removal of Cr(VI) from wastewater. Under optimal adsorption conditions, the maximum adsorption capacity of TTCA/THT@Fe₃O₄ for Cr(VI) can reach 1340 mg∙g^‒1. Notably, the removal efficiency can approach 98.9%, even at the lower concentration of 20 mg∙L^‒1 Cr(VI). For actual wastewater containing Cr(VI), the Cr(VI) concentration was reduced from 25.8 to 0.4 mg∙L^‒1, a remarkable 20% lower than the current industry discharge standard value. A mechanism for the high adsorption performance of Cr(VI) on TTCA/THT@Fe₃O₄ was investigated using Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and density functional theory. It can be plausibly attributed to the formation of Cr/N and Cr/S coordination bonds. Additionally, surface electrostatic adsorption, reduction effects, and the spherical polymer structure increase the contact area with Cr(VI), maximizing adsorption. The synergistic effect of adsorption and reduction enhances the adsorption performance of TTCA/THT@Fe₃O₄ for Cr(VI) and total chromium in water. The resultant polymer has a simple preparation process, excellent adsorption performance, easy magnetic separation, and promising application for actual wastewater.

Keywords magnetic polymer chromium removal hydrogen bonding recyclability actual wastewater

Corresponding Author(s): Jianhui Sun

Just Accepted Date: 07 April 2023 Online First Date: 08 June 2023 Issue Date: 07 October 2023

Cite this article:

Nan Sun,Qing Wu,Lifang Jin, et al. Hyperbranched magnetic polymer: highly efficient removal of Cr(VI) and application in electroplating wastewater[J]. Front. Chem. Sci. Eng., 2023, 17(10): 1568-1580.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2303-2
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I10/1568

Fig.1 (a, b) SEM, (c, d) TEM, and (e–h) elemental mapping images of M-TT; (i) EDS spectrum.

Fig.2 (a) FTIR spectra; (b) XRD pattern; (c) XPS spectrum; (d) magnetic hysteresis loops of M-TT and Fe₃O₄; (e) TGA curves and (f) BET pore size analysis of M-TT and TT.

Tab.1 Comparison of Cr(VI) uptake by various adsorbents

Fig.3 (a) Adsorption and removal efficiencies of Cr(VI) by M-TT (pH = 4.4, t = 298 K); (b) adsorption capacities (q_e) and isotherms at different temperatures with initial concentrations ranging from 10 to 5000 mg?L^?1; (c) effect of contact time on adsorption of Cr(VI) and total chromium (Cr_tot) by M-TT, and (d) the kinetic model; (e) the effect of M-TT dosage on Cr(VI) adsorption (C₀ = 20 mg?L^?1); and (f) zeta potential of M-TT and effect of pH.

Fig.4 (a) The removal performance of heavy metal ions in the mixed solution; (b) cyclic adsorption performance of M-TT for Cr(VI) (pH = 4.4, t = 298 K, C₀ = 20 mg?L^?1); and the effect of (c) pH and (d) dosage on adsorption performance in actual wastewater.

Fig.5 (a) FTIR spectra of M-TT before and after adsorption of Cr(VI); high-resolution XPS spectra of (b) Cr2p, (c) N1s, (d) S2p, and (e) Fe2p after adsorption of Cr(VI); and (f) removal of Cr(VI) by TT and M-TT.

Fig.6 Proposed mechanism of Cr(VI) removal by M-TT.

Fig.7 The optimized geometries of TTCA/THT@Fe₃O₄ monomer, and the structure with Cr: adsorption (a) site 1, (b) site 2, (c) site 3, and (d) site 4; and (e, f) 3D charge difference of Cr atom on substrate material (iso-surface value 0.01 eV?Bohr^?3, and in the 3D plot, the yellow and green regions denote charge accumulation and depletion, respectively).

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