Environmental Science and Pollution Research

, Volume 26, Issue 9, pp 8768–8778 | Cite as

Synergistic effect and degradation mechanism on Fe-Ni/CNTs for removal of 2,4-dichlorophenol in aqueous solution

  • Yufeng Sun
  • Zongtang Liu
  • Zhenghao Fei
  • Changshun Li
  • Yuan Chun
  • Aimin ZhangEmail author
Research Article


Fe-Ni bimetallic nanoparticles supported on CNTs (Fe-Ni/CNTs) were synthesized, characterized, and applied for removal of 2,4-dichlorophenol (2,4-DCP) in aqueous solution. The removal performance was enhanced drastically on Fe-Ni/CNTs with respect to monometallic Fe/CNTs. The synergistic effect between Fe-Ni nanoparticles and CNTs has been studied in detail. The research results indicated that the doping of Ni played an important role in promoting the catalytic degradation of 2,4-DCP. And the presence of CNTs not only could effectively reduce the aggregation of nanoparticles but also facilitate the mass transfer of 2,4-DCP and the formation of active atomic hydrogen during the catalytic process. In addition, the removal kinetics of 2,4-DCP by Fe-Ni/CNTs were in agreement with a pseudo-first-order model, and the rate constants were dependent on a number of factors including the initial concentration of 2,4-DCP, the dosage of Fe-Ni/CNTs, pH value of the solution, and doping amount of Ni. The degradation mechanism involved the adsorption by CNTs and catalytic reduction by Fe under the stimulating of Ni, and the preferred dechlorination followed the order of para-Cl > ortho-Cl. The study confirmed that Fe-Ni/CNTs had a potential to be a promising catalytic material for removal of chlorophenol and had a great prospect for practical application.


Supported Fe-Ni nanoparticles CNTs 2,4-dichlorophenol Degradation Synergistic effect 


Funding Information

This work was financially supported by the National Natural Science Foundation of China (No.41877118 and 21573104), the Natural Science Foundation of Jiangsu Province of China (No.BK20181479), and the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (No.17KJB610013 and 17KJA610006).

Supplementary material

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  1. Bhowmick S, Chakraborty S, Mondal P, Renterghem WV, Berghe SVD, Roman Ross G, Chatterjee D, Iglesias M (2014) Montmorillonite-supported nanoscale zero-valent iron for removal of arsenic from aqueous solution: kinetics and mechanism. Chem Eng J 243:14–23CrossRefGoogle Scholar
  2. Biesinger MC, Payne BP, Grosvenor AP, Lau LWM, Gerson AR, Smart RSC (2011) Resolving surface chemical states in XPS analysis of first row transition metals, oxides, and hydroxides: Cr, Mn, Fe, Co and Ni. Appl Surf Sci 257:2717–2730CrossRefGoogle Scholar
  3. Chaudhary D, Ansari MZ, Khare N, Vankar VD (2017) Preparation, characterization and photocatalytic activity of anatase, rutile TiO2/multiwalled carbon nanotubes nanocomposite for organic dye degradation. J Nanosci Nanotechnol 17:1894–1900CrossRefGoogle Scholar
  4. Chen QQ, Wu PX, Li YY, Zhu NW, Dang Z (2009) Heterogeneous photo-Fenton photodegradation of reactive brilliant orange X-GN over iron-pillared montmorillonite under visible irradiation. J Hazard Mater 168:901–908CrossRefGoogle Scholar
  5. Chen ZX, Jin XY, Chen ZL, Megharaj M, Naidu R (2011) Removal of methyl orange from aqueous solution using bentonite-supported nanoscale zero-valent iron. J Colloid Interf Sci 36:601–607CrossRefGoogle Scholar
  6. Cheng R, Wang JL, Zhang WX (2007) Comparison of reductive dechlorination of p-chlorophenol using Fe0 and nanosized Fe0. J Hazard Mater 144:334–339CrossRefGoogle Scholar
  7. Cheng R, Zhou W, Wang JL, Qi DD, Guo L, Zhang WX, Qian Y (2010) Dechlorination of pentachlorophenol using nanoscale Fe/Ni particles: role of nano-Ni and its size effect. J Hazard Mater 180:79–85CrossRefGoogle Scholar
  8. Contreras S, Rodriguez M, Al Momani F, Sans C, Esplugas S (2003) Contribution of the ozonation pre-treatment to the biodegradation of aqueous solutions of 2,4-dichlorophenol. Water Res 37:3164–3171CrossRefGoogle Scholar
  9. Dolfing J, Harrison BK (1992) Gibbs free energy of formation of halogenated aromatic compounds and their potential role as electron acceptor in anaerobic environments. Environ Sci Technol 26:2213–2216CrossRefGoogle Scholar
  10. Doong RA, Saha S, Lee CH, Lin HP (2015) Mesoporous silica supported bimetallic Pd/Fe for enhanced dechlorination of tetrachloroethylene. RSC Adv 5:90797–90805CrossRefGoogle Scholar
  11. Fang ZQ, Qiu XH, Chen JH, Qiu XQ (2011) Debromination of polybrominated diphenyl ethers by Ni/Fe bimetallic nanoparticles: influencing factors, kinetics, and mechanism. J Hazard Mater 185:958–969CrossRefGoogle Scholar
  12. Fang LP, Xu CH, Zhang WB, Huang LZ (2018) The important role of polyvinylpyrrolidone and Cu on enhancing dechlorination of 2,4-dichlorophenol by Cu/Fe nanoparticles: performance and mechanism study. Appl Surf Sci 435:55–64CrossRefGoogle Scholar
  13. Gao Y, Wang FF, Wu Y, Naidu R, Chen ZL (2016) Comparison of degradation mechanisms of microcystin-LR using nanoscale zero-valent iron (nZVI) and bimetallic Fe/Ni and Fe/Pd nanoparticles. Chem Eng J 285:459–466CrossRefGoogle Scholar
  14. Grosvenor AP, Kobe BA, Biesinger MC, Mcintyre NS (2004) Investigation of multiplet splitting of Fe 2p XPS spectra and bonding in iron compounds. Surf Interface Anal 36:1564–1574CrossRefGoogle Scholar
  15. He YH, Lin H, Dong YB, Li B, Wang L, Chu SY, Luo MK, Liu JF (2018) Zeolite supported Fe/Ni bimetallic nanoparticles for simultaneous removal of nitrate and phosphate: synergistic effect and mechanism. Chem Eng J 347:669–681CrossRefGoogle Scholar
  16. Huang Q, Liu W, Peng PA, Huang WL (2013) Reductive dechlorination of tetrachlorobisphenol A by Pd/Fe bimetallic catalysts. J Hazard Mater 262:634–641CrossRefGoogle Scholar
  17. Kanel SR, Manning B, Charlet L, Choi H (2005) Removal of arsenic(III) from groundwater by nanoscale zero-valent iron. Environ Sci Technol 39:1291–1298CrossRefGoogle Scholar
  18. Kim HS, Lee H, Han KS, Kim JH, Song MS, Park MS, Lee JY, Kang JK (2005) Hydrogen storage in Ni nanoparticle-dispersed multiwalled carbon nanotubes. J Phys Chem B 109:8983–8986CrossRefGoogle Scholar
  19. Kragulj M, Trickovic J, Kukovecz A, Jovic B, Molnar J, Roncevic S, Konya Z, Dalmacija B (2015) Adsorption of chlorinated phenols on multiwalled carbon nanotubes. RSC Adv 5:24920–24929CrossRefGoogle Scholar
  20. Li H, Li HX, Dai WL, Wang WJ, Fang ZG, Deng JF (1999) XPS studies on surface electronic characteristics of Ni-B and Ni-P amorphous alloy and its correlation to their catalytic properties. Appl Surf Sci 152:25–34CrossRefGoogle Scholar
  21. Li YM, Zhang Y, Li JF, Sheng GD, Zheng XM (2013) Enhanced reduction of chlorophenols by nanoscale zerovalent iron supported on organobentonite. Chemosphere 92:368–374CrossRefGoogle Scholar
  22. Li SP, Ma XL, Liu LJ, Cao XH (2015) Degradation of 2,4-dichlorophenol in wastewater by low temperature plasma coupled with TiO2 photocatalysis. RSC Adv 5:1902–1909CrossRefGoogle Scholar
  23. Li H, Qiu YF, Wang XL, Yang J, Yu YJ, Chen YQ, Liu YD (2017) Biochar supported Ni/Fe bimetallic nanoparticles to remove 1,1,1-trichloroethane under various reaction conditions. Chemosphere 169:534–541CrossRefGoogle Scholar
  24. Lin YM, Chen ZL, Megharaj M, Naidu R (2012) Degradation of scarlet 4BS in aqueous solution using bimetallic Fe/Ni nanoparticles. J Colloid Interf Sci 381:30–35CrossRefGoogle Scholar
  25. Liptak MD, Gross KC, Seybold PG, Feldgus S, Shields GC (2002) Absolute pK(a) determinations for substituted phenols. J Am Chem Soc 124:6421–6427CrossRefGoogle Scholar
  26. Liu QS, Zheng T, Wang P, Jiang JP, Li N (2010) Adsorption isotherm, kinetic and mechanism studies of some substituted phenols on activated carbon fibers. Chem Eng J 157:348–356CrossRefGoogle Scholar
  27. Liu XW, Chen ZX, Chen ZL, Megharaj M, Naidu R (2013) Remediation of Direct Black G in wastewater using kaolin-supported bimetallic Fe/Ni nanoparticles. Chem Eng J 223:764–771CrossRefGoogle Scholar
  28. Liu ZT, Gu CG, Ye M, Bian YY, Cheng YW, Wang F, Yang XL, Song Y, Jiang X (2015) Debromination of polybrominated diphenyl ethers by attapulgite-supported Fe/Ni bimetallic nanoparticles: influencing factors, kinetics and mechanism. J Hazard Mater 298:328–337CrossRefGoogle Scholar
  29. Mishra A, Sharma M, Mehta A, Basu S (2017) Microwave treated bentonite clay based TiO2 composites: an efficient photocatalyst for rapid degradation of methylene blue. J Nanosci Nanotechnol 17:1149–1155CrossRefGoogle Scholar
  30. Nagpal V, Bokare AD, Chikate RC, Rode CV, Paknikar KM (2010) Reductive dechlorination of ϒ-hexachlorocyclohexane using Fe-Pd bimetallic nanoparticles. J Hazard Mater 175:680–687CrossRefGoogle Scholar
  31. Nasser A, Mingelgrin U (2014) Birnessite-induced mechanochemical degradation of 2,4-dichlorophenol. Chemosphere 107:175–179CrossRefGoogle Scholar
  32. O’Carroll D, Sleep B, Krol M, Boparai H, Kocur C (2013) Nanoscale zero valent iron and bimetallic particles for contaminated site remediation. Adv Water Resour 51:104–122CrossRefGoogle Scholar
  33. Pulido Melian E, Gonzalez Diaz O, Dona Rodriguez JM, Arana J, Perez Pena J (2013) Adsorption and photocatalytic degradation of 2,4-dichlorophenol in TiO2 suspensions: effect of hydrogen peroxide, sodium peroxodisulphate, and ozone. Appl Catal A Gen 455:227–233CrossRefGoogle Scholar
  34. Sahu RS, Li DL, Doong RA (2018) Unveiling the hydrodechlorination of trichloroethylene by reduced graphene oxide supported bimetallic Fe/Ni nanoparticles. Chem Eng J 334:30–40CrossRefGoogle Scholar
  35. Shih YH, Hsu CY, Su YF (2011) Reduction of hexachlorobenzene by nanoscale zero-valent iron: kinetics, pH effect, and degradation mechanism. Sep Purif Technol 76:268–274CrossRefGoogle Scholar
  36. Solsona B, Concepcion P, Hernandez S, Demicol B, Lopez Nieto JM (2012) Oxidative dehydrogenation of ethane over NiO-CeO2 mixed oxides catalysts. Catal Today 180:51–58CrossRefGoogle Scholar
  37. Song H, Carraway ER (2005) Reduction of chlorinated ethanes by nanosized zero-valent iron: kinetics, pathways, and effects of reaction conditions. Environ Sci Technol 39:6237–6245CrossRefGoogle Scholar
  38. Song SQ, Yang HX, Rao RC, Liu HD, Zhang AM (2010) High catalytic activity and selectivity for hydroxylation of benzene to phenol over multi-walled carbon nanotubes supported Fe3O4 catalyst. Appl Catal A Gen 375:265–271CrossRefGoogle Scholar
  39. Song SQ, Jiang SJ, Rao RC, Yang HX, Zhang AM (2011) Bicomponent VO2-defects/MWCNT catalyst for hydroxylation of benzene to phenol: promoter effect of defects on catalytic performance. Appl Catal A Gen 401:215–219CrossRefGoogle Scholar
  40. Su J, Lin S, Chen ZL, Megharaj M, Naidu R (2011) Dechlorination of p-chlorophenol from aqueous solution using bentonite supported Fe/Pd nanoparticles: synthesis, characterization and kinetics. Desalination 280:167–173CrossRefGoogle Scholar
  41. Sun ZR, Wei XF, Han YB, Tong S, Hu X (2013) Complete dechlorination of 2,4-dichlorophenol in aqueous solution on palladium/polymeric pyrrole-cetyl trimethyl ammonium bromide/foam-nickel composite electrode. J Hazard Mater 244-245:287–294CrossRefGoogle Scholar
  42. Sun YF, Li CS, Zhang AM (2016) Preparation of Ni/CNTs catalyst with high reducibility and their superior catalytic performance in benzene hydrogenation. Appl Catal A Gen 522:180–187CrossRefGoogle Scholar
  43. Tian H, Li JJ, Mu Z, Li LD, Hao ZP (2009) Effect of pH on DDT degradation in aqueous solution using bimetallic Ni/Fe nanoparticles. Sep Purif Technol 66:84–89CrossRefGoogle Scholar
  44. Tsang DCW, Graham NJD, Lo IMC (2009) Humic acid aggregation in zero-valent iron systems and its effects on trichloroethylene removal. Chemosphere 75:1338–1343CrossRefGoogle Scholar
  45. Velu S, Suzuki K, Vijayaraj M, Barman S, Gopinath CS (2005) In situ XPS investigations of Cu1-xNixZnAl-mixed metal oxide catalysts used in the oxidative steam reforming of bio-ethanol. Appl Catal B Environ 55:287–299CrossRefGoogle Scholar
  46. Wei JJ, Xu XH, Liu Y, Wang DH (2006) Catalytic hydrodechlorination of 2,4-dichlorophenol over nanoscale Pd/Fe: reaction pathway and some experimental parameters. Water Res 40:348–354CrossRefGoogle Scholar
  47. Weng XL, Sun Q, Lin S, Chen ZL, Megharaj M, Naidu R (2014) Enhancement of catalytic degradation of amoxicillin in aqueous solution using clay supported bimetallic Fe/Ni nanoparticles. Chemosphere 103:80–85CrossRefGoogle Scholar
  48. Witonska IA, Walock MJ, Binczarski M, Lesiak M, Stanishevsky AV, Karski S (2014) Pd-Fe/SiO2 and Pd-Fe/Al2O3 catalysts for selective hydrodechlorination of 2,4-dichlorophenol into phenol. J Mol Catal A Chem 393:248–256CrossRefGoogle Scholar
  49. Wu PX, Liu CM, Huang ZJ, Wang WM (2014) Enhanced dechlorination performance of 2,4-dichlorophenol by vermiculite supported iron nanoparticles doped with palladium. RSC Adv 4:25580–25587CrossRefGoogle Scholar
  50. Xiao JN, Yue QY, Gao BY, Sun YY, Kong JJ, Gao Y, Li Q, Wang Y (2014) Performance of activated carbon/nanoscale zero-valent iron for removal of trihalomethanes (THMs) at infinitesimal concentration in drinking water. Chem Eng J 253:63–72CrossRefGoogle Scholar
  51. Xu J, Lv XS, Li JD, Li YY, Shen L, Zhou HY, Xu XH (2012) Simultaneous adsorption and dechlorination of 2,4-dichlorophenol by Pd/Fe nanoparticles with multi-walled carbon nanotube support. J Hazard Mater 225-226:36–45CrossRefGoogle Scholar
  52. Xu JL, Li YL, Jing C, Zhang HC, Ning Y (2014) Removal of uranium from aqueous solution using montmorillonite-supported nanoscale zero-valent iron. J Radioanal Nucl Chem 299:329–336CrossRefGoogle Scholar
  53. Yang HX, Song SQ, Rao RC, Wang XZ, Yu Q, Zhang AM (2010) Enhanced catalytic activity of benzene hydrogenation over nickel confined in carbon nanotubes. J Mol Catal A Chem 323:33–39CrossRefGoogle Scholar
  54. Yang M, Ling Q, Rao RC, Yang HX, Zhang QY, Liu HD, Zhang AM (2013) Mn3O4-NiO-Ni/CNTs catalysts prepared by spontaneous redox at high temperature and their superior catalytic performance in selective oxidation of benzyl alcohol. J Mol Catal A Chem 380:61–69CrossRefGoogle Scholar
  55. Zhang Z, Cissoko N, Wo JJ, Xu XH (2009) Factors influencing the dechlorination of 2,4-dichlorophenol by Ni-Fe nanoparticles in the presence of humic acid. J Hazard Mater 165:78–86CrossRefGoogle Scholar
  56. Zhang ZY, Lu M, Zhang ZZ, Xiao M, Zhang M (2012) Dechlorination of short chain chlorinated paraffins by nanoscale zero-valent iron. J Hazard Mater 243:105–111CrossRefGoogle Scholar
  57. Zhou T, Li YZ, Lim TT (2010) Catalytic hydrodechlorination of chlorophenols by Pd/Fe nanoparticles: comparisons with other bimetallic systems, kinetics and mechanism. Sep Purif Technol 76:206–214CrossRefGoogle Scholar
  58. Zhou SM, Li Y, Chen JT, Liu ZM, Wang ZH, Na P (2014) Enhanced Cr(VI ) removal from aqueous solutions using Ni/Fe bimetallic nanoparticles: characterization, kinetics and mechanism. RSC Adv 4:50699–50707CrossRefGoogle Scholar
  59. Zhou ZM, Ruan WJ, Huang HH, Shen CH, Yuan BL, Huang CH (2016) Fabrication and characterization of Fe/Ni nanoparticles supported by polystyrene resin for trichloroethylene degradation. Chem Eng J 283:730–739CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Yufeng Sun
    • 1
    • 2
  • Zongtang Liu
    • 2
  • Zhenghao Fei
    • 2
  • Changshun Li
    • 1
  • Yuan Chun
    • 1
  • Aimin Zhang
    • 1
    Email author
  1. 1.Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical EngineeringNanjing UniversityNanjingPeople’s Republic of China
  2. 2.School of Chemistry and Environmental EngineeringYancheng Teachers UniversityYanchengPeople’s Republic of China

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