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Environmental Science and Pollution Research

, Volume 25, Issue 30, pp 30575–30584 | Cite as

Preparation and application of magnetic nitrogen-doped rGO for persulfate activation

  • Ya Pang
  • Kun Luo
  • Lin Tang
  • Xue Li
  • Yong Song
  • Cheng-yong Li
  • Li-ping Wang
Research Article
  • 74 Downloads

Abstract

A heterogeneous catalyst (M-N-rGO) composed of stability enhanced magnetic iron oxide nanoparticles and nitrogen-doped reduced graphene oxide was synthesized and characterized by SEM, XRD, BET, and XPS. It showed excellent catalytic degradation properties in advanced oxidation technology. In the presence of 200 mg/L catalyst and 135 mg/L persulfate at pH 5, 95% of 10–20 mg/L methylene blue could be degraded in 90 min with the TOC removal efficiency of 50%. The rate constant based on pseudo-first-order kinetics ranged from 0.0227 to 0.0488/min in the temperature range of 15 to 32 °C, and the activation energy was 32.5 kJ/mol. Under the optimal operation conditions, 20 mg/L of 2,4-dichlorophneol (2,4-DCP) could be removed almost completely. EPR analysis showed that sulfate and hydroxyl radicals were responsible for degradation of pollutants, and radical quenching experiments indicated that nonradical pathway also played a role in pollutant removal. And a mechanism for M-N-rGO and persulfate system was elucidated. This catalyst was easy for preparation, low-cost, highly effective, convenient for separation, and could be used effectively for four times through 0.1 mol/L H2SO4 regeneration. It provided a choice for wastewater treatment in practice.

Keywords

Nitrogen-doped graphene oxide Magnetic nanoparticles Sulfate radical Wastewater treatment Advanced oxidation technology 

Notes

Funding information

This work was financially supported by the National Natural Science Foundation of China (No. 51409024, 51579096, 51404041), the Natural Science Foundation of Hu Nan China (2017JJ3341), and science and technology project of Changsha China (ZD1601017, ZD1601058).

Supplementary material

11356_2018_2974_MOESM1_ESM.docx (3.1 mb)
ESM 1 (DOCX 3156 kb)

References

  1. Bu LJ, Zhou SQ, Shi Z, Gao Y (2016) Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways. Environ Sci Pollut Res 23:2848–2855CrossRefGoogle Scholar
  2. Chabot V, Higgins D, Yu A, Chen Z (2014) A review of graphene and graphene oxide sponge: material synthesis and applications to energy and the environment. Energy Environ Sci 7(5):1564–1596CrossRefGoogle Scholar
  3. Cheng X, Guo H, Zhang Y, Liu Y, Liu H (2016) Oxidation of 2,4-dichlorophenol by non-radical mechanism using persulfate activated by Fe/S modified carbon nanotubes. J Colloid Interface Sci 469:277–285CrossRefGoogle Scholar
  4. Duan XG, O'Donnell K, Sun HQ, Wang YX, Wang SB (2015a) Sulfur and nitrogen co-doped graphene for metal-free catalytic oxidation reactions. Small 11(25):3036–3044CrossRefGoogle Scholar
  5. Duan X, Ao Z, Sun H, Indrawirawan S (2015b) Nitrogen-doped graphene for generation and evolution of reactive radicals by metal-free catalysis. ACS Appl Mater Interfaces 7(7):4169–4174CrossRefGoogle Scholar
  6. Duan X, Sun H, Tade M, Wang S (2018) Metal-free activation of persulfate by cubic mesoporouscarbons for catalytic oxidation via radical and nonradical processes. Catal Today 307:140–146CrossRefGoogle Scholar
  7. Fang GD, Gao J, Dionysios DD, Zhou M (2013) Activation of persulfate by quinones: free radical reactions and implication for the degradation of PCBs. Environ Sci Technol 47:4605–4611CrossRefGoogle Scholar
  8. George PA, Dionysiou DD (2003) Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt. Environ Sci Technol 37:4790–4797CrossRefGoogle Scholar
  9. Hung C, Chen C, Zhe Y, Huang J, Dong C (2016a) Fe3O4 magnetic nanoparticles: characterization and performance exemplified by the degradation of methylene blue in the presence of persulfate. J Adv Oxid Technol 19(1):43–51Google Scholar
  10. Hung CM, Chen C, Liu Y, Dong CD (2016b) Decolorization of methylene blue by persulfate activated with FeO magnetic particles. Water Environ Res 88:675–686CrossRefGoogle Scholar
  11. Ji F, Li CL, Wei XY, Yu J (2013) Efficient performance of porous Fe2O3 in heterogeneous activation of peroxymonosulfate for decolorization of rhodamine B. Chem Eng J 231:434–440CrossRefGoogle Scholar
  12. Jiang C, Ji Y, Shi Y, Chen J, Cai T (2016) Sulfate radical-based oxidation of fluoroquinolone antibiotics: kinetics, mechanisms and effects of natural water matrices. Water Res 106:507–513CrossRefGoogle Scholar
  13. Kang J, Duan X, Zhou L, Tadé MO, Wang S (2016) Carbocatalytic activation of persulfate for removal of antibiotics in water solutions. Chem Eng J 288:399–405CrossRefGoogle Scholar
  14. Lee H, Lee HJ, Lee C (2015) Activation of persulfates by carbon nanotubes: oxidation of organic compounds by nonradical mechanism. Chem Eng J 266:28–33CrossRefGoogle Scholar
  15. Li J, Lin H, Zhu KM, Zhang H (2017) Degradation of Acid Orange 7 using peroxymonosulfate catalyzed by granulated activated carbon and enhanced by electrolysis. Chemosphere 188:139–147CrossRefGoogle Scholar
  16. Lin KA, Chen BJ, Chen CK (2016) Evaluating Prussian blue analogues MII3[MIII (CN)6]2 (MII = Co, Cu, Fe, Mn, Ni; MIII = Co, Fe) as activators for peroxymonosulfate in water. RSC Adv 6:92923–92933CrossRefGoogle Scholar
  17. Liu CS, Shih K, Sun CX, Wang F (2012) Oxidative degradation of propachlor by ferrous and copper ion activated persulfate. Sci Total Environ 416:507–513CrossRefGoogle Scholar
  18. Matzek W, Carte K (2016) Activated persulfate for organic chemical degradation: a review. Chemosphere 151:178–188CrossRefGoogle Scholar
  19. Nidheesh PV (2017) Graphene-based materials supported advanced oxidation processes for water and wastewater treatment: a review. Environ Sci Pollut Res 24:27047–27069CrossRefGoogle Scholar
  20. Ocampo MA (2009) Persulfate activation by organic compounds. Dissertation, Washington State UniversityGoogle Scholar
  21. Oh WD, Dong Z, Lim TT (2016) Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: current development, challenges and prospects. Appl Catal B Environ 194:169–201CrossRefGoogle Scholar
  22. Pang Y, Zeng GM, Tang L, Zhang Y, Liu YY (2011) Preparation and application of stability enhanced magnetic nanoparticles for rapid removal of Cr (VI). Chem Eng J 175:222–227CrossRefGoogle Scholar
  23. Peng S, Guo HL, Peng S, Ning SK (2012) Preparation of nitrogen-doped graphene and its supercapacitive properties. Acta Phys -Chim Sin 28(11):2745–2753Google Scholar
  24. Pu M, Ma Y, Wan J, Wang Y, Huang M (2014) Fe/S doped granular activated carbon as a highly active heterogeneous persulfate catalyst toward the degradation of Orange G and diethylphthalate. J Colloid Interface Sci 418:330–337CrossRefGoogle Scholar
  25. Qi CD, Wei QX, Qu S, Xia SQ (2015) Degradation and dechlorination of pentachlorophenol by microwave-activated persulfate. Environ Sci Pollut Res 22:4670–4679CrossRefGoogle Scholar
  26. Rastogi A, Al-Abed SR, Dionysiou DD (2009) Sulfate radical-based ferrous peroxymonosulfate oxidative system for PCBs degradation in aqueous and sediment systems. Appl Catal B Environ 85:171–179CrossRefGoogle Scholar
  27. Scott-Emuakpor EO, Kruth A, Todd MJ, Raab A, Macphee DE (2012) Remediation of 2,4-dichlorophenol contaminated water by visible light-enhanced WO3 photoelectrocatalysis. Appl Catal B Environ 123-124:433–439CrossRefGoogle Scholar
  28. Sing KS (1989) The use of gas adsorption for the characterization of porous solids. Colloids Surf 38:113–124CrossRefGoogle Scholar
  29. Sun L, Wang L, Tian CG, Fu HG (2012) Nitrogen-doped graphene with high nitrogen level via a one-step hydrothermal reaction of graphene oxide with urea for superior capacitive energy storage. RSC Adv 2:4498–4506CrossRefGoogle Scholar
  30. Sun HQ, Kwan CK, Suvorova A (2014) Catalytic oxidation of organic pollutants on pristine and surface nitrogen-modified carbon nanotubes with sulfate radicals. Appl Catal B Environ 154-155:134–141CrossRefGoogle Scholar
  31. Tan C, Deng Y, Zhou S (2014) Radical induced degradation of acetaminophen with Fe3O4 magnetic nanoparticles as heterogeneous activator of Peroxymonosulfate. J Hazard Mater 276(9):452–460CrossRefGoogle Scholar
  32. Wang H, Yuan XZ, Zeng GM, Wu Y (2015a) Three dimensional graphene based materials: synthesis and applications from energy storage and conversion to electrochemical sensor and environmental remediation. Adv Colloid Interface Sci 221:41–59CrossRefGoogle Scholar
  33. Wang X, Qin Y, Tang H (2015b) Nitrogen-doped reduced graphene oxide as a bifunctional material for removing bisphenols: synergistic effect between adsorption and catalysis. Environ Sci Technol 49(11):6855–6864CrossRefGoogle Scholar
  34. Xu XR and Li X Z (2010) Degradation of azo dye Orange G in aqueous solutions by persulfate with ferrous ion. Sep. Puri. Technol, 72: 105–111CrossRefGoogle Scholar
  35. Yang S, Yang X, Shao X, Wang L (2011) Activated carbon catalyzed persulfate oxidation of Azo dye acid orange 7 at ambient temperature. J Hazard Mater 186(1):659–666CrossRefGoogle Scholar
  36. Zhang T, Chen Y, Yang Y (2014) Efficient peroxydisulfate activation process not relying on sulfate radical generation for water pollutant degradation. Environ Sci Technol 48:5868–5876CrossRefGoogle Scholar
  37. Zhang X, Feng M, Qu R, Wang L (2016) Catalytic degradation of diethyl phthalate in aqueous solution by persulfate activated with nano-scaled magnetic CuFe2O4/MWCNTs. Chem Eng J 301:1–11CrossRefGoogle Scholar
  38. Zhang KJ, Zhou X, Zhang TQ, Li C (2018) Degradation of the earthy and musty odorant 2,4,6-tricholoroanisole by persulfate activated with iron of different valences. Environ Sci Pollut Res 25:3435–3445CrossRefGoogle Scholar
  39. Zhao QX, Mao QM, Zhou YY, Wei JH, Tang L (2017) Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: a review on heterogeneous catalysts and applications. Chemosphere 189:224–238CrossRefGoogle Scholar
  40. Zhou L, Ma J, Zhang H, Shao Y, Li Y (2015a) Fabrication of magnetic carbon composites from peanut shells and its application as a heterogeneous Fenton catalyst in removal of methylene blue. Appl Surf Sci 324:490–498CrossRefGoogle Scholar
  41. Zhou Y, Yen CH, Fu S, Zhu C (2015b) One-pot synthesis of B-doped three dimensional reduced graphene oxide via supercritical fluid for oxygen reduction reaction. Green Chem 17(6):3552–3560CrossRefGoogle Scholar
  42. Zhu HL, Yang D, Zhu M, Yao KH (2007) A facile two-step hydrothermal route for the synthesis of -Fe2O3 nanocrystals and their magnetic properties. J Mater Sci 42:9205–9209CrossRefGoogle Scholar
  43. Zhu CG, Fang GD, Dionysios DD, Liu C (2016) Efficient transformation of DDTs with persulfate activation by zero-valent iron nanoparticles: a mechanistic study. J Hazard Mater 316:232–241CrossRefGoogle Scholar
  44. Zrinyi N, Pham AL (2017) Oxidation of benzoic acid by heat-activated persulfate: effect of temperature on transformation pathway and product distribution. Water Res 120:43–52CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.College of Biology and Environmental EngineeringChangsha UniversityChangshaChina
  2. 2.Department of Agricultural and Biological EngineeringUniversity of FloridaGainesvilleUSA
  3. 3.College of Environmental Science and EngineeringHunan universityChangshaChina

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