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Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2020, Vol. 14 Issue (6) : 1006-1017     https://doi.org/10.1007/s11705-020-1924-y
RESEARCH ARTICLE
Immobilization of nano-zero-valent irons by carboxylated cellulose nanocrystals for wastewater remediation
Bangxian Peng1, Rusen Zhou2, Ying Chen1, Song Tu1, Yingwu Yin1, Liyi Ye1()
1. Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
2. School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Brisbane, QLD 4000, Australia
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Abstract

Nano-zero-valent irons (nZVI) have shown great potential to function as universal and low-cost magnetic adsorbents. Yet, the rapid agglomeration and easy surface corrosion of nZVI in solution greatly hinders their overall applicability. Here, carboxylated cellulose nanocrystals (CCNC), widely available from renewable biomass resources, were prepared and applied for the immobilization of nZVI. In doing so, carboxylated cellulose nanocrystals supporting nano-zero-valent irons (CCNC-nZVI) were obtained via an in-situ growth method. The CCNC-nZVI were characterized and then evaluated for their performances in wastewater treatment. The results obtained show that nZVI nanoparticles could attach to the carboxyl and hydroxyl groups of CCNC, and well disperse on the CCNC surface with a size of ~10 nm. With the CCNC acting as corrosion inhibitors improving the reaction activity of nZVI, CCNC-nZVI exhibited an improved dispersion stability and electron utilization efficacy. The Pb(II) adsorption capacity of CCNC-nZVI reached 509.3 mg·g1 (298.15 K, pH= 4.0), significantly higher than that of CCNC. The adsorption was a spontaneous exothermic process and could be perfectly fitted by the pseudo-second-order kinetics model. This study may provide a novel and green method for immobilizing magnetic nanomaterials by using biomass-based resources to develop effective bio-adsorbents for wastewater decontamination.

Keywords carboxylated cellulose nanocrystals      nano-zero-valent irons      magnetic bio-adsorbents      wastewater remediation     
Corresponding Author(s): Liyi Ye   
Just Accepted Date: 17 March 2020   Online First Date: 14 April 2020    Issue Date: 11 September 2020
 Cite this article:   
Bangxian Peng,Rusen Zhou,Ying Chen, et al. Immobilization of nano-zero-valent irons by carboxylated cellulose nanocrystals for wastewater remediation[J]. Front. Chem. Sci. Eng., 2020, 14(6): 1006-1017.
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http://journal.hep.com.cn/fcse/EN/10.1007/s11705-020-1924-y
http://journal.hep.com.cn/fcse/EN/Y2020/V14/I6/1006
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Bangxian Peng
Rusen Zhou
Ying Chen
Song Tu
Yingwu Yin
Liyi Ye
Fig.1  Scheme 1 Diagram highlighting the preparation process of CCNC-nZVI and the application as absorbents for Pb(II) removal.
Fig.2  (a) SEM, (b) TEM, (c) XRD characterization of CCNC, and (d) the Zeta potential of CCNC (inset shows the size distribution of CCNC at pH= 7).
Fig.3  (a) FTIR spectra of MCC, CCNC, nZVI and CCNC-nZVI; (b) XRD patterns of nZVI, CCNC-nZVI before and after Pb(II) adsorption (CCNC-nZVI-Pb).
Fig.4  SEM images of (a) nZVI and (b) CCNC-nZVI; TEM images of (c) nZVI and (d) CCNC-nZVI; (e) size distribution and (f) N2 adsorption/desorption isotherms of nZVI and CCNC-nZVI; (g) VSM curves of nZVI and CCNC-nZVI and (h) photographs of nZVI and CNCC-nZVI in aqueous solutions for a certain time after synthesized (3 min and 72 h).
Fig.5  (a) Effects of adsorption time and mass ratio of CCNC and nZVI in the CCNC-nZVI composites on Pb(II) adsorption capacity, (b) residual content of iron and lead in solutions after adsorption for 2 h, (c) effect of initial pH on adsorption and (d) Pb(II) content, (e) effect of initial concentration on Pb(II) adsorption of CCNC-nZVI (1:1) and (f) regeneration experiment of CCNC-nZVI (1:1).
Fig.6  (a) Pseudo-first-order and (b) pseudo-second-order kinetic models for adsorption (m = 0.4 g·L−1, C0 = 100 mg·L−1, pH= 4.0, temperature= 298.15 K); (c) Langmuir and (d) Freundlich isothermal models for adsorption at various temperatures (m = 0.4 g·L−1, pH= 4.0).
Pseudo-first order Pseudo-second order
qe /(mg·g−1) k1 R2 qe /(mg·g−1) k2 R2
249.75 –0.03 0.956 250.00 0.004 0.999
Tab.1  Kinetic parameters for Pb(II) adsorption on CCNC-nZVI
Temperature /K Langmuir Freundlich
qmax /(mg·g−1) KL/(L·mg−1) R2 KF/(mg·g−1) n R2
298.15 653.59 0.23 0.941 149.26 3.60 0.896
308.15 581.40 0.24 0.990 131.57 3.69 0.975
318.15 505.05 0.14 0.985 102.20 3.76 0.993
Tab.2  Isotherm parameters for Pb(II) adsorption on CCNC-nZVI
Adsorbent Initial pH T/°C Qm /(mg·g−1) Ref.
Amino-functionalized magnetic sludge-biochar 5.5 25 127.0 [39]
Hollow Fe3O4@PDA nanoparticles 5.0 25 57.25 [40]
Magnetite-decorated Si-Schiff base complex 5.0 25 133.64 [38]
Activated carbon supported zero-valent iron composite 6.0 25 59.35 [41]
Oxidized mesoporous carbon from asphalt and aluminum isopropoxide 6.5 30 277.8 [37]
Chitosan nanoparticle 5.0 25 94.34 [42]
Chitin nanofibers 5.0 25 60.24 [42]
Magnetic Fe3O4-mesporous magnesium silicate 5.0 43 247.5 [43]
Sepiolite-supported nanoscale zero-valent iron 6.0 28 44.05 [44]
Zero valent iron magnetic biochar composites 6.0 30 60.8 [45]
CCNC-nZVI 4.0 25 653.59 This work
Tab.3  Comparison of the maximum Pb(II) adsorption capacity on various adsorbents
Fig.7  (a) XPS full-scan surveys; (b) Pb 4f spectrum of CCNC-nZVI after Pb(II) adsorption; Fe 2p spectra of CCNC-nZVI (c) before and (d) after Pb(II) adsorption; O 1s spectra of CCNC-nZVI (e) before and (f) after Pb(II) adsorption.
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