Environmental Science and Pollution Research

, Volume 24, Issue 10, pp 9651–9661 | Cite as

Excellent performance of cobalt-impregnated activated carbon in peroxymonosulfate activation for acid orange 7 oxidation

  • Tianyin Huang
  • Jiabin ChenEmail author
  • Zhongming Wang
  • Xin Guo
  • John C. CrittendenEmail author
Research Article


Cobalt-impregnated activated carbon (GAC/Co) was used to produce sulfate radical (SO4 ·) from peroxymonosulfate (PMS) in aqueous solution (hereafter called PMS activation). We evaluated its effectiveness by examining the degradation of orange acid 7 (AO7). GAC/Co exhibited high activity to activate PMS to degrade AO7. The degradation efficiency of AO7 increased with increasing dosage of GAC/Co or PMS and elevated temperatures. pH 8 was most favorable for the degradation of AO7 by GAC/Co-activated PMS. The radical quenching experiments indicated that the reactions most likely took place both in the bulk solution and on the surface of GAC/Co. We found that SO4 · played a dominant role in AO7 degradation. Sodium chloride (NaCl) which presents in most dye wastewater had a significant impact on AO7 degradation. Low dosages (<0.4 M) of NaCl showed a slight inhibitory effect, whereas high dosages (0.8 M) increased the reaction rate. HOCl was confirmed as the main contributor for accelerating AO7 degradation with high concentration of NaCl. In a continuous-flow reaction with an empty-bed contact time of 1.35 min, AO7 was not detected in the effluent for 0 to 18.72 L of treated influent volume (156 h) and 85% removal efficiency was still observed after 40.32 L of treated volume (336 h). Finally, the azo bond and the naphthalene structure in AO7 were destroyed and the degradation pathway was proposed.


Peroxymonosulfate Orange acid 7 Activated carbon Cobalt Chloride 



We sincerely thank the National Natural Science Foundation of China (51478283, 51509175) for financially supporting this work. The authors appreciate support from the Brook Byers Institute for Sustainable Systems (BBISS), Hightower Chair and Georgia Research Alliance at Georgia Institute of Technology.

Supplementary material

11356_2017_8648_MOESM1_ESM.docx (1 mb)
ESM 1 (DOCX 1058 kb)


  1. Ahn YY, Yun ET, Seo JW, Lee C, Kim SH, Kim JH, Lee J (2016) Activation of peroxymonosulfate by surface-loaded noble metal nanoparticles for oxidative degradation of organic compounds. Environ Sci Technol 50:10187–10197CrossRefGoogle Scholar
  2. Anipsitakis GP, Dioniou DD (2004) Radical generation by the interaction of transition metals with common oxidants. Environ Sci Technol 38:3705–3712CrossRefGoogle Scholar
  3. Anipsitakis GP, Dionysiou DD, Gonzalez MA (2006) Cobalt-mediated activation of peroxymonosulfate and sulfate radical attack on phenolic compounds. Implications of chloride ions. Environ Sci Technol 40:1000–1007CrossRefGoogle Scholar
  4. Antoniou MG, de la Cruz AA, Dionysiou DD (2010) Degradation of microcystin-LR using sulfate radicals generated through photolysis, thermolysis and e transfer mechanisms. Appl Catal B Environ 96:290–298CrossRefGoogle Scholar
  5. Azam A, Hamid A (2006) Effects of gap size and UV dosage on decolorization of C.I. Acid Orange 7 by UV/H2O2 process. J Hazard Mater 133:167–171CrossRefGoogle Scholar
  6. Bakheet B, Yuan S, Li Z, Wang H, Zuo J, Komarneni S, Wang Y (2013) Electro-peroxone treatment of Orange II dye wastewater. Water Res 47:6234–6243CrossRefGoogle Scholar
  7. Bauer C, Jacques P, Kalt A (2001) Photooxidation of an azo dye induced by visible light incident on the surface of TiO2. J Photoch Photobio A 140:87–92CrossRefGoogle Scholar
  8. Brillas E, Martinez-Huitle CA (2015) Decontamination of wastewaters containing synthetic organic dyes by electrochemical methods. An updated review. Appl Catal B Environ 166:603–643CrossRefGoogle Scholar
  9. Cai C, Wang L, Gao H, Hou L, Zhang H (2014a) Ultrasound enhanced heterogeneous activation of peroxydisulfate by bimetallic Fe-Co/GAC catalyst for the degradation of acid Orange 7 in water. J Environ Sci 26:1267–1273CrossRefGoogle Scholar
  10. Cai C, Zhang H, Zhong X, Hou L (2014b) Electrochemical enhanced heterogeneous activation of peroxydisulfate by Fe–Co/SBA-15 catalyst for the degradation of Orange II in water. Water Res 66:473–485CrossRefGoogle Scholar
  11. Cai C, Zhang H, Zhong X, Hou L (2015) Ultrasound enhanced heterogeneous activation of peroxymonosulfate by a bimetallic Fe–Co/SBA-15 catalyst for the degradation of Orange II in water. J Hazard Mater 283:70–79CrossRefGoogle Scholar
  12. Chan KH, Chu W (2009) Degradation of atrazine by cobalt-mediated activation of peroxymonosulfate: different cobalt counteranions in homogenous process and cobalt oxide catalysts in photolytic heterogeneous process. Water Res 43:2513–2521CrossRefGoogle Scholar
  13. Chen XY, Chen JW, Qiao XL, Wang DG, Cai XY (2008) Performance of nano-Co3O4/peroxymonosulfate system: kinetics and mechanism study using acid Orange 7 as a model compound. Appl Catal B Environ 80:116–121CrossRefGoogle Scholar
  14. Chen J, Hong W, Huang T, Zhang L, Li W, Wang Y (2016a) Activated carbon fiber for heterogeneous activation of persulfate: implication for the decolorization of azo dye. Environ Sci Pollut Res 23:18564–18574CrossRefGoogle Scholar
  15. Chen J, Qian Y, Liu H, Huang T (2016b) Oxidative degradation of diclofenac by thermally activated persulfate: implication for ISCO. Environ Sci Pollut Res 23:3824–3833CrossRefGoogle Scholar
  16. Chen J, Zhang L, Huang T, Li W, Wang Y, Wang Z (2016c) Decolorization of azo dye by peroxymonosulfate activated by carbon nanotube: radical versus non-radical mechanism. J Hazard Mater 320:571–580CrossRefGoogle Scholar
  17. Feng W, Nansheng D, Helin H (2000) Degradation mechanism of azo dye C.I. reactive red 2 by iron powder reduction and photooxidation in aqueous solutions. Chemosphere 41:1233–1238CrossRefGoogle Scholar
  18. Feng Y, Liu J, Wu D, Zhou Z, Deng Y, Zhang T, Shih K (2015) Efficient degradation of sulfamethazine with CuCo2O4 spinel nanocatalysts for peroxymonosulfate activation. Chem Eng J 280:514–524CrossRefGoogle Scholar
  19. Gao H, Chen J, Zhang Y, Zhou X (2016) Sulfate radicals induced degradation of Triclosan in thermally activated persulfate system. Chem Eng J 306:522–530CrossRefGoogle Scholar
  20. Garcia-Segura S, Dosta S, Guilemany JM, Brillas E (2013) Solar photoelectrocatalytic degradation of acid Orange 7 azo dye using a highly stable TiO2 photoanode synthesized by atmospheric plasma spray. Appl Catal B Environ 132:142–150CrossRefGoogle Scholar
  21. Ghanbari F, Moradi M (2017) Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: review. Chem Eng J 310:41–62CrossRefGoogle Scholar
  22. Grčić I, Papić S, Koprivanac N, Kovačić I (2012) Kinetic modeling and synergy quantification in sono and photooxidative treatment of simulated dyehouse effluent. Water Res 46:5683–5695CrossRefGoogle Scholar
  23. Guan YH, Ma J, Li XC, Fang JY, Chen LW (2011) Influence of pH on the formation of sulfate and hydroxyl radicals in the UV/peroxymonosulfate system. Environ Sci Technol 45:9308–9314CrossRefGoogle Scholar
  24. Guan YH, Ma J, Ren YM, Liu YL, Xiao JY, Lin LQ, Zhang C (2013) Efficient degradation of atrazine by magnetic porous copper ferrite catalyzed peroxymonosulfate oxidation via the formation of hydroxyl and sulfate radicals. Water Res 47:5431–5438CrossRefGoogle Scholar
  25. Han F, Kambala VSR, Srinivasan M, Rajarathnam D, Naidu R (2009) Tailored titanium dioxide photocatalysts for the degradation of organic dyes in wastewater treatment: a review. Appl Catal A Gen 359:25–40CrossRefGoogle Scholar
  26. He X, de la Cruz AA, O'Shea KE, Dionysiou DD (2014) Kinetics and mechanisms of cylindrospermopsin destruction by sulfate radical-based advanced oxidation processes. Water Res 63:168–178CrossRefGoogle Scholar
  27. Huling SG, Ko S, Park S, Kan E (2011) Persulfate oxidation of MTBE- and chloroform-spent granular activated carbon. J Hazard Mater 192:1484–1490CrossRefGoogle Scholar
  28. Ji Y, Dong C, Kong D, Lu J (2015) New insights into atrazine degradation by cobalt catalyzed peroxymonosulfate oxidation: kinetics, reaction products and transformation mechanisms. J Hazard Mater 285:491–500CrossRefGoogle Scholar
  29. Kan E, Huling SG (2009) Effects of temperature and acidic pre-treatment on Fenton-driven oxidation of MTBE-spent granular activated carbon. Environ Sci Technol 43:1493–1499CrossRefGoogle Scholar
  30. Lee YC, Lo SL, Kuo J, Huang CP (2013) Promoted degradation of perfluorooctanic acid by persulfate when adding activated carbon. J Hazard Mater 261:463–469CrossRefGoogle Scholar
  31. Lee H, Lee HJ, Jeong J, Lee J, Park NB, Lee C (2015) Activation of persulfates by carbon nanotubes: oxidation of organic compounds by nonradical mechanism. Chem Eng J 266:28–33CrossRefGoogle Scholar
  32. Liang C, Su HW (2009) Identification of sulfate and hydroxyl radicals in thermally activated persulfate. Ind Eng Chem Res 48:5558–5562CrossRefGoogle Scholar
  33. Liang C, Lin YT, Shin WH (2009a) Persulfate regeneration of trichloroethylene spent activated carbon. J Hazard Mater 168:187–192CrossRefGoogle Scholar
  34. Liang CJ, Lin YT, Shih WH (2009b) Treatment of trichloroethylene by adsorption and persulfate oxidation in batch studies. Ind Eng Chem Res 48:8373–8380CrossRefGoogle Scholar
  35. Liang Y, Li Y, Wang H, Zhou J, Wang J, Regier T, Dai H (2011) Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat Mater 10:780–786CrossRefGoogle Scholar
  36. Mahdi Ahmed M, Barbati S, Doumenq P, Chiron S (2012) Sulfate radical anion oxidation of diclofenac and sulfamethoxazole for water decontamination. Chem Eng J 197:440–447CrossRefGoogle Scholar
  37. Mezohegyi G, van der Zee FP, Font J, Fortuny A, Fabregat A (2012) Towards advanced aqueous dye removal processes: a short review on the versatile role of activated carbon. J Environ Manag 102:148–164CrossRefGoogle Scholar
  38. Muhammad S, Shukla PR, Tadé MO, Wang S (2012) Heterogeneous activation of peroxymonosulphate by supported ruthenium catalysts for phenol degradation in water. J Hazard Mater 215–216:183–190CrossRefGoogle Scholar
  39. Neta P, Maruthamuthu P, Carton PM (1978) Formation and reactivity of the amino radical. J Phys Chem 82:1875–1878CrossRefGoogle Scholar
  40. Nfodzo P, Choi H (2011) Triclosan decomposition by sulfate radicals: effects of oxidant and metal doses. Chem Eng J 174:629–634CrossRefGoogle Scholar
  41. Oh WD, Lua SK, Dong Z, Lim TT (2015) Performance of magnetic activated carbon composite as peroxymonosulfate activator and regenerable adsorbent via sulfate radical-mediated oxidation processes. J Hazard Mater 284:1–9CrossRefGoogle Scholar
  42. Peng Y, Fu D, Liu R, Zhang F, Liang X (2008) NaNO2/FeCl3 catalyzed wet oxidation of the azo dye acid Orange 7. Chemosphere 71:990–997CrossRefGoogle Scholar
  43. Qian Y, Zhou X, Zhang Y, Sun P, Zhang W, Chen J, Guo X, Zhang X (2015) Performance of alpha-methylnaphthalene degradation by dual oxidant of persulfate/calcium peroxide: implication for ISCO. Chem Eng J 279:538–546CrossRefGoogle Scholar
  44. Qian Y, Guo X, Zhang Y, Peng Y, Sun P, Huang CH, Niu J, Zhou X, Crittenden JC (2016) Perfluorooctanoic acid degradation using UV–persulfate process: modeling of the degradation and chlorate formation. Environ Sci Technol 50:772–781CrossRefGoogle Scholar
  45. Qiang Z, Adams CD (2004) Determination of Mmonochloramine formation rate constants with stopped-flow spectrophotometry. Environ Sci Technol 38:1435–1444CrossRefGoogle Scholar
  46. Shi PH, Dai XF, Zheng HG, Li DX, Yao WF, Hu CY (2014) Synergistic catalysis of Co3O4 and graphene oxide on Co3O4/GO catalysts for degradation of Orange II in water by advanced oxidation technology based on sulfate radicals. Chem Eng J 240:264–270CrossRefGoogle Scholar
  47. Shukla PR, Wang SB, Sun HQ, Ang HM, Tade M (2010) Activated carbon supported cobalt catalysts for advanced oxidation of organic contaminants in aqueous solution. Appl Catal B Environ 100:529–534CrossRefGoogle Scholar
  48. Shukla P, Sun H, Wang S, Ang HM, Tadé MO (2011) Co-SBA-15 for heterogeneous oxidation of phenol with sulfate radical for wastewater treatment. Catal Today 175:380–385CrossRefGoogle Scholar
  49. Szpyrkowicz L, Juzzolino C, Kaul SN (2001) A comparative study on oxidation of disperse dyes by electrochemical process, ozone, hypochlorite and Fenton reagent. Water Res 35:2129–2136CrossRefGoogle Scholar
  50. Valdes H, Zaror CA (2006) Ozonation of benzothiazole saturated-activated carbons: influence of carbon chemical surface properties. J Hazard Mater 137:1042–1048CrossRefGoogle Scholar
  51. Wang P, Yang S, Shan L, Niu R, Shao X (2011) Involvements of chloride ion in decolorization of acid Orange 7 by activated peroxydisulfate or peroxymonosulfate oxidation. J Environ Sci 23:1799–1807CrossRefGoogle Scholar
  52. Wu J, Zhang H, Qiu J (2012) Degradation of acid Orange 7 in aqueous solution by a novel electro/Fe2+/peroxydisulfate process. J Hazard Mater 215–216:138–145CrossRefGoogle Scholar
  53. Yang Q, Choi H, Dionysiou DD (2007) Nanocrystalline cobalt oxide immobilized on titanium dioxide nanoparticles for the heterogeneous activation of peroxymonosulfate. Appl Catal B Environ 74:170–178CrossRefGoogle Scholar
  54. Yang S, Wang P, Yang X, Shan L, Zhang W, Shao X, Niu R (2010) Degradation efficiencies of azo dye acid Orange 7 by the interaction of heat, UV and anions with common oxidants: persulfate, peroxymonosulfate and hydrogen peroxide. J Hazard Mater 179:552–558CrossRefGoogle Scholar
  55. Yang S, Yang X, Shao X, Niu R, Wang L (2011) Activated carbon catalyzed persulfate oxidation of azo dye acid orange 7 at ambient temperature. J Hazard Mater 186:659–666CrossRefGoogle Scholar
  56. Yeddou AR, Nadjemi B, Halet F, Ould-Dris A, Capart R (2010) Removal of cyanide in aqueous solution by oxidation with hydrogen peroxide in presence of activated carbon prepared from olive stones. Miner Eng 23:32–39CrossRefGoogle Scholar
  57. Yuan RX, Ramjaun SN, Wang ZH, Liu JS (2011) Effects of chloride ion on degradation of acid Orange 7 by sulfate radical-based advanced oxidation process: implications for formation of chlorinated aromatic compounds. J Hazard Mater 196:173–179CrossRefGoogle Scholar
  58. Zhang B, Cho M, Fortner JD, Lee J, Huang CH, Hughes JB, Kim JH (2009) Delineating oxidative processes of aqueous C-60 preparations: role of THF peroxide. Environ Sci Technol 43:108–113CrossRefGoogle Scholar
  59. Zhang J, Shao XT, Shi C, Yang SY (2013a) Decolorization of acid Orange 7 with peroxymonosulfate oxidation catalyzed by granular activated carbon. Chem Eng J 232:259–265CrossRefGoogle Scholar
  60. Zhang T, Zhu H, Croué JP (2013b) Production of sulfate radical from peroxymonosulfate induced by a magnetically separable CuFe2O4 spinel in water: efficiency, stability, and mechanism. Environ Sci Technol 47:2784–2791CrossRefGoogle Scholar
  61. Zhang BT, Zhang Y, Teng YH, Fan MH (2015a) Sulfate radical and its application in decontamination technologies. Crit Rev Env Sci Tec 45:1756–1800CrossRefGoogle Scholar
  62. Zhang Q, Chen J, Dai C, Zhang Y, Zhou X (2015b) Degradation of carbamazepine and toxicity evaluation using the UV/persulfate process in aqueous solution. J Chem Technol Biot 90:701–708CrossRefGoogle Scholar
  63. Zhao HZ, Sun Y, Xu LN, Ni JR (2010) Removal of acid Orange 7 in simulated wastewater using a three-dimensional electrode reactor: removal mechanisms and dye degradation pathway. Chemosphere 78:46–51CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  1. 1.School of Environmental Science and EngineeringSuzhou University of Science and TechnologySuzhouPeople’s Republic of China
  2. 2.Brook Byers Institute for Sustainable Systems and the School of Civil and Environmental EngineeringGeorgia Institute of TechnologyAtlantaUSA

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