Please wait a minute...
Shopping Cart Email List Chinese
Advanced Search Fig/Tab
Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

Featured Articles  |  Most Downloaded  |  Most Reading
Online Submission Subscribe to Our RSS Content Feed
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
 Download: PDF(2183 KB)   HTML
 Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
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·g−1 (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.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-1924-y
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I6/1006
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.
1 L Ouni, A Ramazani, S Taghavi Fardood. An overview of carbon nanotubes role in heavy metals removal from wastewater. Frontiers of Chemical Science and Engineering, 2019, 13(2): 274–295
https://doi.org/10.1007/s11705-018-1765-0
2 R B Fu, Y P Yang, Z Xu, X Zhang, X P Guo, D S Bi. The removal of chromium (VI) and lead (II) from groundwater using sepiolite-supported nanoscale zero-valent iron (S-NZVI). Chemosphere, 2015, 138: 726–734
https://doi.org/10.1016/j.chemosphere.2015.07.051
3 B Chen, C Zhu, J Fei, Y Jiang, C Yin, W Su, X He, Y Li, Q Chen, Q Ren, Y Chen. Reaction kinetics of phenols and p-nitrophenols in flowing aerated aqueous solutions generated by a discharge plasma jet. Journal of Hazardous Materials, 2019, 363: 55–63
https://doi.org/10.1016/j.jhazmat.2018.09.051
4 M Nahata, C Y Seo, P Krishnakumar, J Schwank. New approaches to water purification for resource-constrained settings: Production of activated biochar by chemical activation with diammonium hydrogenphosphate. Frontiers of Chemical Science and Engineering, 2018, 12(1): 194–208
https://doi.org/10.1007/s11705-017-1647-x
5 Y Yan, P Huang, H P Zhang. Preparation and characterization of novel carbon molecular sieve membrane/PSSF composite by pyrolysis method for toluene adsorption. Frontiers of Chemical Science and Engineering, 2019, 13(4): 772–783
https://doi.org/10.1007/s11705-019-1827-y
6 Q Q Tao, X Zhang, K Prabaharan, Y Dai. Separation of cesium from wastewater with copper hexacyanoferrate film in an electrochemical system driven by microbial fuel cells. Bioresource Technology, 2019, 278: 456–459
https://doi.org/10.1016/j.biortech.2019.01.093
7 R S Zhou, R W Zhou, X H Zhang, K Bazaka, K Ostrikov. Continuous flow removal of acid fuchsine by dielectric barrier discharge plasma water bed enhanced by activated carbon adsorption. Frontiers of Chemical Science and Engineering, 2019, 13(2): 340–349
https://doi.org/10.1007/s11705-019-1798-z
8 F L Fu, D D Dionysiou, H Liu. The use of zero-valent iron for groundwater remediation and wastewater treatment: A review. Journal of Hazardous Materials, 2014, 267: 194–205
https://doi.org/10.1016/j.jhazmat.2013.12.062
9 F Yang, S S Zhang, Y Q Sun, K Cheng, J S Li, D C W Tsang. Fabrication and characterization of hydrophilic corn stalk biochar-supported nanoscale zero-valent iron composites for efficient metal removal. Bioresource Technology, 2018, 265: 490–497
https://doi.org/10.1016/j.biortech.2018.06.029
10 Z Q Cai, J Fu, P H Du, X Zhao, X D Hao, W Liu, D Y Zhao. Reduction of nitrobenzene in aqueous and soil phases using carboxymethyl cellulose stabilized zero-valent iron nanoparticles. Chemical Engineering Journal, 2018, 332: 227–236
https://doi.org/10.1016/j.cej.2017.09.066
11 P Dhar, A Kumar, V Katiyar. Fabrication of cellulose nanocrystal supported stable Fe(0) nanoparticles: A sustainable catalyst for dye reduction, organic conversion and chemo-magnetic propulsion. Cellulose (London, England), 2015, 22(6): 3755–3771
https://doi.org/10.1007/s10570-015-0759-z
12 X Zhao, W Liu, Z Q Cai, B Han, T W Qian, D Y Zhao. An overview of preparation and applications of stabilized zero-valent iron nanoparticles for soil and groundwater remediation. Water Research, 2016, 100: 245–266
https://doi.org/10.1016/j.watres.2016.05.019
13 Y Mu, F Jia, Z H Ai, L Z Zhang. Iron oxide shell mediated environmental remediation properties of nano zero-valent iron. Environmental Science. Nano, 2017, 4(1): 27–45
https://doi.org/10.1039/C6EN00398B
14 W Liu, S T Tian, X Zhao, W B Xie, Y Y Gong, D Y Zhao. Application of stabilized nanoparticles for in situ remediation of metal-contaminated soil and groundwater: A critical review. Current Pollution Reports, 2015, 1(4): 280–291
https://doi.org/10.1007/s40726-015-0017-x
15 L N Shi, Y M Lin, X Zhang, Z L Chen. Synthesis, characterization and kinetics of bentonite supported nZVI for the removal of Cr (VI) from aqueous solution. Chemical Engineering Journal, 2011, 171(2): 612–617
https://doi.org/10.1016/j.cej.2011.04.038
16 N Horzum, M M Demir, M Nairat, T Shahwan. Chitosan fiber-supported zero-valent iron nanoparticles as a novel sorbent for sequestration of inorganic arsenic. RSC Advances, 2013, 3(21): 7828–7837
https://doi.org/10.1039/c3ra23454a
17 H R Dong, J M Deng, Y K Xie, C Zhang, Z Jiang, Y J Cheng, K J Hou, G M Zeng. Stabilization of nanoscale zero-valent iron (nZVI) with modified biochar for Cr (VI) removal from aqueous solution. Journal of Hazardous Materials, 2017, 332: 79–86
https://doi.org/10.1016/j.jhazmat.2017.03.002
18 Z Q Cai, J Fu, P H Du, X Zhao, X D Hao, W Liu, D Y Zhao. Reduction of nitrobenzene in aqueous and soil phases using carboxymethyl cellulose stabilized zero-valent iron nanoparticles. Chemical Engineering Journal, 2018, 332: 227–236
https://doi.org/10.1016/j.cej.2017.09.066
19 X S Lv, J Xu, G M Jiang, X H Xu. Removal of chromium (VI) from wastewater by nanoscale zero-valent iron particles supported on multiwalled carbon nanotubes. Chemosphere, 2011, 85(7): 1204–1209
https://doi.org/10.1016/j.chemosphere.2011.09.005
20 L Brinchi, F Cotana, E Fortunati, J M Kenny. Production of nanocrystalline cellulose from lignocellulosic biomass: Technology and applications. Carbohydrate Polymers, 2013, 94(1): 154–169
https://doi.org/10.1016/j.carbpol.2013.01.033
21 S S Jiang, H Daly, H Xiang, Y Yan, H P Zhang, C Hardacre, X L Fan. Microwave-assisted catalyst-free hydrolysis of fibrous cellulose for deriving sugars and biochemical. Frontiers of Chemical Science and Engineering, 2019, 13(4): 718–726
https://doi.org/10.1007/s11705-019-1804-5
22 M S Islam, L Chen, J Sisler, K C Tam. Cellulose nanocrystal (CNC)–inorganic hybrid systems: Synthesis, properties and applications. Journal of Materials Chemistry. B, Materials for Biology and Medicine, 2018, 6(6): 864–883
https://doi.org/10.1039/C7TB03016A
23 H Maimaiti, A Awati, G Yisilamu, D D Zhang, S X Wang. Synthesis and visible-light photocatalytic CO2/H2O reduction to methyl formate of TiO2 nanoparticles coated by aminated cellulose. Applied Surface Science, 2019, 466: 535–544
https://doi.org/10.1016/j.apsusc.2018.10.070
24 S Zarei, M Niad, H Raanaei. The removal of mercury ion pollution by using Fe3O4-nanocellulose: Synthesis, characterizations and DFT studies. Journal of Hazardous Materials, 2018, 344: 258–273
https://doi.org/10.1016/j.jhazmat.2017.10.009
25 H Liu, J Song, S B Shang, Z Q Song, D Wang. Cellulose nanocrystal/silver nanoparticle composites as bifunctional nanofillers within waterborne polyurethane. ACS Applied Materials & Interfaces, 2012, 4(5): 2413–2419
https://doi.org/10.1021/am3000209
26 L Chen, W J Cao, P J Quinlan, R M Berry, K C Tam. Sustainable catalysts from gold-loaded polyamidoamine dendrimer-cellulose nanocrystals. ACS Sustainable Chemistry & Engineering, 2015, 3(5): 978–985
https://doi.org/10.1021/acssuschemeng.5b00110
27 M Cheng, Z Y Qin, Y Y Chen, J M Liu, Z C Ren. Facile one-step extraction and oxidative carboxylation of cellulose nanocrystals through hydrothermal reaction by using mixed inorganic acids. Cellulose (London, England), 2017, 24(8): 3243–3254
https://doi.org/10.1007/s10570-017-1339-1
28 J A Avila Ramirez, E Fortunati, J M Kenny, L Torre, M L Foresti. Simple citric acid-catalyzed surface esterification of cellulose nanocrystals. Carbohydrate Polymers, 2017, 157: 1358–1364
https://doi.org/10.1016/j.carbpol.2016.11.008
29 J Lu, P Askeland, L T Drzal. Surface modification of microfibrillated cellulose for epoxy composite applications. Polymer, 2008, 49(5): 1285–1296
https://doi.org/10.1016/j.polymer.2008.01.028
30 C J Zhou, Q L Wu, Y Y Yue, Q G Zhang. Application of rod-shaped cellulose nanocrystals in polyacrylamide hydrogels. Journal of Colloid and Interface Science, 2011, 353(1): 116–123
https://doi.org/10.1016/j.jcis.2010.09.035
31 X L Yu, S R Tong, M F Ge, L Y Wu, J C Zuo, C Y Cao, W G Song. Adsorption of heavy metal ions from aqueous solution by carboxylated cellulose nanocrystals. Journal of Environmental Sciences (China), 2013, 25(5): 933–943
https://doi.org/10.1016/S1001-0742(12)60145-4
32 X Zhang, S Lin, Z L Chen, M Megharaj, R Naidu. Kaolinite-supported nanoscale zero-valent iron for removal of Pb2+ from aqueous solution: Reactivity, characterization and mechanism. Water Research, 2011, 45(11): 3481–3488
https://doi.org/10.1016/j.watres.2011.04.010
33 L M Wu, L B Liao, G C Lv, F X Qin, Y J He, X Y Wang. Micro-electrolysis of Cr (VI) in the nanoscale zero-valent iron loaded activated carbon. Journal of Hazardous Materials, 2013, 254-255: 277–283
https://doi.org/10.1016/j.jhazmat.2013.03.009
34 L Ling, B C Pan, W X Zhang. Removal of selenium from water with nanoscale zero-valent iron: Mechanisms of intraparticle reduction of Se (IV). Water Research, 2015, 71: 274–281
https://doi.org/10.1016/j.watres.2015.01.002
35 K D Gong, Q Hu, Y Y Xiao, X Cheng, H Liu, N Wang, B Qiu, Z H Guo. Triple layered core-shell ZVI@carbon@polyaniline composite enhanced electron utilization in Cr(VI) reduction. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2018, 6(24): 11119–11128
https://doi.org/10.1039/C8TA03066A
36 F C Su, H J Zhou, Y X Zhang, G Z Wang. Three-dimensional honeycomb-like structured zero-valent iron/chitosan composite foams for effective removal of inorganic arsenic in water. Journal of Colloid and Interface Science, 2016, 478: 421–429
https://doi.org/10.1016/j.jcis.2016.06.035
37 X L Zhang, Q L Lin, S Y Luo, K Z Ruan, K P Peng. Preparation of novel oxidized mesoporous carbon with excellent adsorption performance for removal of malachite green and lead ion. Applied Surface Science, 2018, 442: 322–331
https://doi.org/10.1016/j.apsusc.2018.02.148
38 A Khan, J Xing, A M Elseman, P C Gu, K Gul, Y J Ai, R Jehan, A Alsaedi, T Hayat, X K Wang. A novel magnetite nanorod-decorated Si-Schiff base complex for efficient immobilization of U(VI) and Pb(II) from water solutions. Dalton Transactions (Cambridge, England), 2018, 43(33): 11327–11336
https://doi.org/10.1039/C8DT01213J
39 X Huang, D Wei, X W Zhang, D W Fan, X Sun, B Du, Q Wei. Synthesis of amino-functionalized magnetic aerobic granular sludge-biochar for Pb(II) removal: Adsorption performance and mechanism studies. Science of the Total Environment, 2019, 685: 681–689
https://doi.org/10.1016/j.scitotenv.2019.05.429
40 N Wang, D X Yang, X X Wang, S J Yu, H Q Wang, T Wen, G Song, Z M Yu, X K Wang. Highly efficient Pb(II) and Cu(II) removal using hollow Fe3O4@PDA nanoparticles with excellent application capability and reusability. Inorganic Chemistry Frontiers, 2018, 5(9): 2174–2182
https://doi.org/10.1039/C8QI00541A
41 X J Liu, D G Lai, Y Wang. Performance of Pb(II) removal by an activated carbon supported nanoscale zero-valent iron composite at ultralow iron content. Journal of Hazardous Materials, 2019, 361: 37–48
https://doi.org/10.1016/j.carbpol.2016.10.085
42 M Siahkamari, A Jamali, A Sabzevari, A Shakeri. Removal of lead(II) ions from aqueous solutions using biocompatible polymeric nano-adsorbents: A comparative study. Carbohydrate Polymers, 2017, 157: 1180–1189
https://doi.org/10.1016/j.jhazmat.2019.120974
43 Z F Zhao, X Zhang, H J Zhou, G Liu, M G Kong, G Z Wang. Microwave-assisted synthesis of magnetic Fe3O4-mesoporous magnesium silicate core-shell composites for the removal of heavy metal ions. Microporous and Mesoporous Materials, 2017, 242: 50–58
https://doi.org/10.1016/j.micromeso.2017.01.006
44 R B Fu, Y P Yang, Z Xu, X Zhang, X P Guo, D S Bi. The removal of chromium (VI) and lead (II) from groundwater using sepiolite-supported nanoscale zero-valent iron (S-NZVI). Chemosphere, 2015, 138: 726–734
https://doi.org/10.1016/j.chemosphere.2015.07.051
45 M Rama Chandraiah. Facile synthesis of zero valent iron magnetic biochar composites for Pb(II) removal from the aqueous medium. Alexandria Engineering Journal, 2016, 55: 619–625
https://doi.org/10.1016/j.jenvman.2016.04.034
46 X Q Li, W X Zhang. Equestration of metal cations with zerovalent iron nanoparticles—a study with high resolution X-ray photoelectron spectroscopy (HR-XPS). Journal of Physical Chemistry C, 2007, 111(19): 6939–6946
https://doi.org/10.1021/jp0702189
47 H W Abdel-Samad, P R Watson. An XPS study of the adsorption of chromate on goethite (α-FeOOH). Applied Surface Science, 1997, 108(3): 371–377
https://doi.org/10.1016/S0169-4332(96)00609-5
48 C Noubactep. A critical review on the process of contaminant removal in Fe0-H2O systems. Environmental Technology, 2008, 29(8): 909–920
https://doi.org/10.1080/09593330802131602
49 J E Martin, A A Herzing, W L Yan, X Q Li, B E Koel, C J Kiely, W X Zhang. Determination of the oxide layer thickness in core-shell zerovalent iron nanoparticles. Langmuir, 2008, 24(8): 4329–4334
https://doi.org/10.1021/la703689k
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed