Transactions of Tianjin University

, Volume 25, Issue 6, pp 567–575 | Cite as

Catalytic Activity of Cr(VI) in the Degradation of Phenol by H2O2 Under Acidic Conditions

  • Qingyou Zeng
  • Shaoyi Jia
  • Yufeng Gong
  • Songhai Wu
  • Xu HanEmail author
Research Article


Cr(VI) and phenol are toxic contaminants that need to be treated, and different methods have been researched to simultaneously remove these two contaminants from industrial wastewater. In this study, Cr(VI) was used as a novel Fenton-like catalyst in phenol degradation by H2O2. In the pH range of 3.0‒11.0, the degradation efficiency of phenol decreased with elevated pH. At pH = 3.0, 100 mg/L phenol was effectively degraded by 2 mmol/L Cr(VI) and 20 mmol/L H2O2. At pH = 7.0 and the same conditions as those of pH = 3.0, 79% of 100 mg/L phenol was removed within 6 h, which was an improvement in pH limitation compared with the Fe(II)-mediated Fenton reaction. Quenching experiments indicated that ·OH generated from the catalysis of H2O2 by Cr(V) instead of Cr(VI) was the primary oxidant that degraded phenol. When pyrophosphate was added in the Cr(VI)/H2O2 system, complexes with the Cr(V) intermediate rapidly formed and inhibited H2O2 decomposition, implying that the decomposition of H2O2 to ·OH was catalyzed by Cr(V) instead of Cr(VI). The presence of anions such as chloride and sulfate had insignificant effect on the degradation of phenol. TOC and UV analyses suggest that phenol could not be completely oxidized to CO2 and H2O, and the intermediates identified by high performance liquid chromatography further indicates that maleic acid and benzoquinone were intermediates which may be further degraded into short chain acids, primarily maleic, formic, acetic, and oxalic acids, and eventually into CO2 and H2O. Considering that more than 50% Cr(VI) can also be removed during this process, the Cr(VI)/H2O2 system is more appropriate for the simultaneous removal of Cr(VI) and phenol contaminants from industrial wastewater.


Cr(VI) Cr(V) Phenol Fenton Simultaneous degradation 



This study was supported by the National Natural Science Foundation of China (No. 41373114 and 51508384), the Natural Science Foundation of Tianjin (No. 15JCZDJC40200), and the Foundation of Key Lab of Indoor Air Environment Quality Control (Tianjin University).

Supplementary material

12209_2018_182_MOESM1_ESM.docx (892 kb)
Supplementary material 1 (DOCX 892 kb)


  1. 1.
    Busca G, Berardinelli S, Resini C et al (2008) Technologies for the removal of phenol from fluid streams: a short review of recent developments. J Hazard Mater 160(2–3):265–288CrossRefGoogle Scholar
  2. 2.
    Ahmed S, Rasul MG, Martens WN et al (2010) Heterogeneous photocatalytic degradation of phenols in wastewater: a review on current status and developments. Desalination 261(1–2):3–18CrossRefGoogle Scholar
  3. 3.
    Kang N, Lee DS, Yoon J (2002) Kinetic modeling of Fenton oxidation of phenol and monochlorophenols. Chemosphere 47(9):915–924CrossRefGoogle Scholar
  4. 4.
    Andreozzi R, Caprio V, Insola A et al (1999) Advanced oxidation processes (AOP) for water purification and recovery. Catal Today 53(1):51–59CrossRefGoogle Scholar
  5. 5.
    Pera-Titus M, García-Molina V, Baños MA et al (2004) Degradation of chlorophenols by means of advanced oxidation processes: a general review. Appl Catal B 47(4):219–256CrossRefGoogle Scholar
  6. 6.
    Garrido-Ramírez EG, Theng BKG, Mora ML (2010) Clays and oxide minerals as catalysts and nanocatalysts in Fenton-like reactions—a review. Appl Clay Sci 47(3–4):182–192CrossRefGoogle Scholar
  7. 7.
    Heckert EG, Seal S, Self WT (2008) Fenton-like reaction catalyzed by the rare earth inner transition metal cerium. Environ Sci Technol 42(13):5014–5019CrossRefGoogle Scholar
  8. 8.
    Salem IA, El-Maazawi MS (2000) Kinetics and mechanism of color removal of methylene blue with hydrogen peroxide catalyzed by some supported alumina surfaces. Chemosphere 41(8):1173–1180CrossRefGoogle Scholar
  9. 9.
    Chaliha S, Bhattacharyya KG (2008) Wet oxidative method for removal of 2,4,6-trichlorophenol in water using Fe(III), Co(II), Ni(II) supported MCM41 catalysts. J Hazard Mater 150(3):728–736CrossRefGoogle Scholar
  10. 10.
    Duarte F, Maldonado-Hódar FJ, Pérez-Cadenas AF et al (2009) Fenton-like degradation of azo-dye Orange II catalyzed by transition metals on carbon aerogels. Appl Catal B Environ 85(3–4):139–147CrossRefGoogle Scholar
  11. 11.
    Bokare AD, Choi W (2010) Chromate-induced activation of hydrogen peroxide for oxidative degradation of aqueous organic pollutants. Environ Sci Technol 44(19):7232–7237CrossRefGoogle Scholar
  12. 12.
    Liu LD, Wang WM, Liu L et al (2016) Catalytic activities of dissolved and Sch-immobilized Mo in H2O2 decomposition: implications for phenol oxidation under acidic conditions. Appl Catal B 185:371–377CrossRefGoogle Scholar
  13. 13.
    Vander Griend DA, Golden JS, Arrington CA Jr (2002) Kinetics and mechanism of chromate reduction with hydrogen peroxide in base. Inorg Chem 41(26):7042–7048CrossRefGoogle Scholar
  14. 14.
    Perez-Benito JF, Arias C (1997) A kinetic study of the chromium (VI) hydrogen peroxide reaction: role of the diperoxochromate (VI) intermediates. J Phys Chem A 101(26):4726–4733CrossRefGoogle Scholar
  15. 15.
    Song H, Liu Y, Xu W et al (2009) Simultaneous Cr(VI) reduction and phenol degradation in pure cultures of Pseudomonas aeruginosa CCTCC AB91095. Biores Technol 100(21):5079–5084CrossRefGoogle Scholar
  16. 16.
    Bagchi D, Stohs SJ, Downs BW et al (2002) Cytotoxicity and oxidative mechanisms of different forms of chromium. Toxicology 180(1):5–22CrossRefGoogle Scholar
  17. 17.
    Wang Z, Bush RT, Sullivan LA et al (2013) Simultaneous redox conversion of chromium(VI) and arsenic(III) under acidic conditions. Environ Sci Technol 47(12):6486–6492CrossRefGoogle Scholar
  18. 18.
    Li Y, Liu LD, Liu L et al (2016) Efficient oxidation of phenol by persulfate using manganite as a catalyst. J Mol Catal A Chem 411:264–271CrossRefGoogle Scholar
  19. 19.
    Han X, Wong YS, Wong MH et al (2007) Biosorption and bioreduction of Cr(VI) by a microalgal isolate, Chlorella miniata. J Hazard Mater 146(1–2):65–72CrossRefGoogle Scholar
  20. 20.
    Wang WM, Song J, Han X (2013) Schwertmannite as a new Fenton-like catalyst in the oxidation of phenol by H2O2. J Hazard Mater 262:412–419CrossRefGoogle Scholar
  21. 21.
    Kotaś J, Stasicka Z (2000) Chromium occurrence in the environment and methods of its speciation. Environ Pollut 107(3):263–283CrossRefGoogle Scholar
  22. 22.
    Park D, Yun YS, Park JM (2004) Reduction of hexavalent chromium with the brown seaweed Ecklonia biomass. Environ Sci Technol 38(18):4860–4864CrossRefGoogle Scholar
  23. 23.
    Pettine M, Campanella L, Millero FJ (2002) Reduction of hexavalent chromium by H2O2 in acidic solutions. Environ Sci Technol 36(5):901–907CrossRefGoogle Scholar
  24. 24.
    Kuznetsova NI, Kuznetsova LI, Likholobov VA (1996) Catalytic properties of Cr-containing heteropolytungstates in H2O2 participated reactions: H2O2 decomposition and oxidation of unsaturated hydrocarbons with H2O2. J Mol Catal A Chem 108(3):135–143CrossRefGoogle Scholar
  25. 25.
    Zhang L, Lay PA (1998) EPR spectroscopic studies on the formation of chromium(V) peroxo complexes in the reaction of chromium(VI) with hydrogen peroxide. Inorg Chem 37:1729–1733CrossRefGoogle Scholar
  26. 26.
    Sugden KD, Wetterhahn KE (1996) EPR evidence for chromium(V) binding to phosphate and pyrophosphate: implications for chromium(V) DNA interactions. Inorg Chem 35(13):3727–3728CrossRefGoogle Scholar
  27. 27.
    Maciel R, Sant’Anna GL Jr, Dezotti M (2004) Phenol removal from high salinity effluents using Fenton’s reagent and photo-Fenton reactions. Chemosphere 57(7):711–719CrossRefGoogle Scholar
  28. 28.
    De Laat J, Le Truong G, Legube B (2004) A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2. Chemosphere 55(5):715–723CrossRefGoogle Scholar
  29. 29.
    Gallard H, De Laat J (2000) Kinetic modelling of Fe(III)/H2O2 oxidation reactions in dilute aqueous solution using atrazine as a model organic compound. Water Res 34(12):3107–3116CrossRefGoogle Scholar
  30. 30.
    Santos A, Yustos P, Quintanilla A (2002) Route of the catalytic oxidation of phenol in aqueous phase. Appl Catal B Environ 39(2):97–113CrossRefGoogle Scholar
  31. 31.
    Liu L, Liu H, Zhao YP et al (2008) Directed synthesis of hierarchical nanostructured TiO2 catalysts and their morphology-dependent photocatalysis for phenol degradation. Environ Sci Technol 42(7):2342–2348CrossRefGoogle Scholar
  32. 32.
    Zazo JA, Casas JA, Mohedano AF (2005) Chemical pathway and kinetics of phenol oxidation by Fenton’s reagent. Environ Sci Technol 39(23):9295–9302CrossRefGoogle Scholar

Copyright information

© Tianjin University and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Qingyou Zeng
    • 1
  • Shaoyi Jia
    • 1
  • Yufeng Gong
    • 2
  • Songhai Wu
    • 1
  • Xu Han
    • 3
    Email author
  1. 1.School of Chemical Engineering and TechnologyTianjin UniversityTianjinChina
  2. 2.College of Environmental Science and EngineeringTongji UniversityShanghaiChina
  3. 3.Key Lab of Indoor Air Environment Quality Control, School of Environmental Science and EngineeringTianjin UniversityTianjinChina

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