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Fabrication of a double-layer membrane cathode based on modified carbon nanotubes for the sequential electro-Fenton oxidation of p-nitrophenol

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Abstract

To improve the electrocatalytic efficiency of the cathode and provide a wider pH range in the electro-Fenton process, N-doped multi-walled carbon nanotubes (NCNTs) and ferrous ion complexed with carboxylated carbon nanotubes (CNT-COOFe2+) were used to fabricate the diffusion layer and catalyst layer of a membrane cathode, respectively. The morphology, structure, and composition of CNT-COOFe2+ were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The oxygen reduction performance of NCNT was evaluated using cyclic voltammetry (CV) and the rotating disk electrode technique (RDE). In addition, a potential application of the cathode in sequential electro-Fenton degradation of p-nitrophenol (p-NP) was investigated. The results revealed that iron was successfully doped on the carboxylated carbon nanotubes in ionic complexation form and the content of iron atoms in CNT-COOFe2+ was 2.65%. Furthermore, the defects on the tube walls provided more reactive sites for the electro-Fenton process. A combination of CV and RDE data indicated that NCNT had better electrocatalytic H2O2 generation activity with a more positive onset potential and higher cathodic peak current response than CNT. A p-NP removal rate of 96.04% was achieved within 120 min, and a mineralization efficiency of 80.26% was obtained at 180 min in the sequential electro-Fenton process at a cathodic potential of − 0.7 V vs SCE and neutral pH. The activity of the used cathode was restored simply through electro-reduction at − 1.0 V vs SCE, and a p-NP removal rate of more than 70% was obtained at 60 min after six regeneration cycles.

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References

  • Ammar S, Oturan M, Labiadh L, Guersalli A, Abdelhedi R, Oturan N, Brillas E (2015) Degradation of tyrosol by a novel electro-Fenton process using pyrite as heterogeneous source of iron catalyst. Water Res 74:77–87

    CAS  Google Scholar 

  • Baba Y, Yatagai T, Harada T, Kawase Y (2015) Hydroxyl radical generation in the photo-Fenton process: effects of carboxylic acids on iron redox cycling. Chem Eng J 277:229–241

    CAS  Google Scholar 

  • Bañuelos JA, El-Ghenymy A, Rodríguez FJ, Manríquez J, Bustos E, Rodríguez A, Brillas E, Godínez LA (2014) Study of an air diffusion activated carbon packed electrode for an electro-Fenton wastewater treatment. Electrochim Acta 140:412–418

    Google Scholar 

  • Brillas E, Sirés I, Oturan MA (2009) Electro-Fenton process and related electrochemical technologies based on Fenton's reaction chemistry. Chem Rev 109(12):6570–6631

    CAS  Google Scholar 

  • Chen WS, Huang CP (2014) Decomposition of nitrotoluenes in wastewater by sonoelectrochemical and sonoelectro-Fenton oxidation. Ultrason Sonochem 21(2):840–845

    CAS  Google Scholar 

  • Duan XY, Ma F, Chang LM (2012) Electrochemical degradation of 4-chlorophenol in aqueous solution using modified PbO2 anode. Water Sci Technol 66(11):2468–2474

    CAS  Google Scholar 

  • Edwards ER, Antunes EF, Botelho EC, Baldan MR, Corat EJ (2011) Evaluation of residual iron in carbon nanotubes purified by acid treatments. Appl Surf Sci 258(2):641–648

    CAS  Google Scholar 

  • Gao GD, Zhang QY, Hao ZW, Vecitis CD (2015) Carbon nanotube membrane stack for flow-through sequential regenerative electro-Fenton. Environ Sci Technol 49(4):2375–2383

    CAS  Google Scholar 

  • Guelfi DR, Gozzi F, Sirés I, Brillas E, Machulek A Jr, Oliveira SC (2019) Antituberculosis drug isoniazid degraded by electro-Fenton and photoelectro-Fenton processes using a boron-doped diamond anode and a carbon-PTFE air-diffusion cathode. Environ Sci Pollut Res 26(5):4415–4425

    CAS  Google Scholar 

  • He HQ, Zhou Z (2017) Electro-Fenton process for water and wastewater treatment. Crit Rev Environ Sci Technol 47(21):2100–2131

    CAS  Google Scholar 

  • Isarain-Chávez E, Arias C, Cabot PL, Centellas F, Rodríguez RM, Garrido JA, Brillas E (2010) Mineralization of the drug β-blocker atenolol by electro-Fenton and photoelectro-Fenton using an air-diffusion cathode for H2O2 electrogeneration combined with a carbon-felt cathode for Fe2+ regeneration. Appl Catal B-Environ 96(3–4):361–369

    Google Scholar 

  • Jiang YH, Hu ZX, Zhou MH, Zhou L, Xi BD (2014) Efficient degradation of p-nitrophenol by electro-oxidation on Fe doped Ti/TiO2 nanotube/PbO2 anode. Sep Purif Technol 128:67–71

    CAS  Google Scholar 

  • Jiang WL, Xia X, Han JL, Ding YC, Haider MR, Wang AJ (2018) Graphene modified electro-Fenton catalytic membrane for in situ degradation of antibiotic florfenicol. Environ Sci Technol 52(17):9972–9982

    CAS  Google Scholar 

  • Lai B, Chen ZY, Zhou YX, Yang P, Wang JL, Chen ZQ (2013) Removal of high concentration p-nitrophenol in aqueous solution by zero valent iron with ultrasonic irradiation (US-ZVI). J Hazard Mater 250-251:220–228

    CAS  Google Scholar 

  • Lan HC, Li JF, Sun M, An XQ, Hu CZ, Liu RP, Liu HJ, Qu JH (2016) Efficient conversion of dimethylarsinate into arsenic and its simultaneous adsorption removal over FeCx/N-doped carbon fiber composite in an electro-Fenton process. Water Res 100:57–64

    CAS  Google Scholar 

  • Lee GW, Kim J, Yoon J, Bae JS, Shin BC, Kim IS, Oh W, Ree M (2008) Structural characterization of carboxylated multi-walled carbon nanotubes. Thin Solid Films 516:5781–5784

    CAS  Google Scholar 

  • Li HL, Lei HY, Yu Q, Li Z, Feng X, Yang BJ (2010) Effect of low frequency ultrasonic irradiation on the sonoelectro-Fenton degradation of cationic red X-GRL. Chem Eng J 160(2):417–422

    CAS  Google Scholar 

  • Li XH, Chen S, Angelidaki I, Zhang YF (2018) Bio-electro-Fenton processes for wastewater treatment: advances and prospects. Chem Eng J 354:492–506

    CAS  Google Scholar 

  • Li B, Yan ZY, Liu XN, Tang C, Zhou J, Wu XY, Wei P, Jia HH, Yong XY (2019) Enhanced bio-electro-Fenton degradation of phenolic compounds based on a novel Fe-Mn/graphite felt composite cathode. Chemosphere 234:260–268

    CAS  Google Scholar 

  • Lin YY, Tonni AK, Ahmad B, Gavin W (2018) Enhanced removal of acetaminophen from synthetic wastewater using multi-walled carbon nanotubes (MWCNTs) chemically modified with NaOH, HNO3/H2SO4, ozone, and/or chitosan. J Mol Liq 251:369–377

    CAS  Google Scholar 

  • Liu K, Yu JC, Dong H, Wu JCS, Hoffmann MR (2018) Degradation and mineralization of carbamazepine using an electro-Fenton reaction catalyzed by magnetite nanoparticles fixed on an electrocatalytic carbon fiber textile cathode. Environ Sci Technol 52(21):12667–12674

    CAS  Google Scholar 

  • Liu K, Yu ML, Wang HY, Wang J, Liu WP, Hoffmann MR (2019) Multiphase porous electrochemical catalysts derived from iron-based metal-organic framework compounds. Environ Sci Technol 53(11):6474–6482

    CAS  Google Scholar 

  • Meijide J, Rosales E, Pazos M, Sanromán MA (2017) p-Nitrophenol degradation by electro-Fenton process: pathway, kinetic model and optimization using central composite design. Chemosphere 185:726–736

    CAS  Google Scholar 

  • Moreira F, Garcia-Segura S, Vilar V, Boaventura R, Brillas E (2013) Decolorization and mineralization of Sunset Yellow FCF azo dye by anodic oxidation, electro-Fenton, UVA photoelectro-Fenton and solar photoelectro-Fenton processes. Appl Catal B-Environ 142-143(10):877–890

    CAS  Google Scholar 

  • Naeimi H, Mohajeri A, Moradi L, Rashidi AM (2009) Efficient and facile one pot carboxylation of multiwalled carbon nanotubes by using oxidation with ozone under mild conditions. Appl Surf Sci 256(3):631–635

    CAS  Google Scholar 

  • Nawaz F, Cao HB, Xie YB, Xiao JD, Chen Y, Ghazi ZA (2017) Selection of active phase of MnO2 for catalytic ozonation of 4-nitrophenol. Chemosphere 168:1457–1466

    CAS  Google Scholar 

  • Oturan M, Sirés I, Oturan N, Pérocheau S, Laborde JL, Trévin S (2008) Sonoelectro-Fenton process: a novel hybrid technique for the destruction of organic pollutants in water. J Electroanal Chem 624(1–2):329–332

    CAS  Google Scholar 

  • Oturan M, Pimentel M, Oturan N, Sirés I (2009) Reaction sequence for the mineralization of the short-chain carboxylic acids usually formed upon cleavage of aromatics during electrochemical Fenton treatment. Electrochim Acta 54(2):173–182

    Google Scholar 

  • Peng Y, Liu HW (2006) Effects of oxidation by hydrogen peroxide on the structures of multiwalled carbon nanotubes. Ind Eng Chem Res 45:6483–6488

    CAS  Google Scholar 

  • Pérez JF, Galia A, Rodrigo MA, Llanos J, Sabatino S, Sáez C, Schiavo B, Scialdone O (2017a) Effect of pressure on the electrochemical generation of hydrogen peroxide in undivided cells on carbon felt electrodes. Electrochim Acta 248:169–177

    Google Scholar 

  • Pérez JF, Llanos J, Sáez C, López C, Cañizares P, Rodrigo MA (2017b) The jet aerator as oxygen supplier for the electrochemical generation of H2O2. Electrochim Acta 246:466–474

    Google Scholar 

  • Poza-Nogueiras V, Rosales E, Pazos M, Sanromán M (2018) Current advances and trends in electro-Fenton process using heterogeneous catalysts - a review. Chemosphere 201:399–416

    CAS  Google Scholar 

  • Sirés I, Brillas E, Oturan M, Rodrigo M, Panizza M (2014) Electrochemical advanced oxidation processes: today and tomorrow. A review. Environ Sci Pollut Res 21(14):8336–8367

    Google Scholar 

  • Tang Q, Wang D, Yao DM, Yang CW, Sun YC (2016) Highly efficient electro-generation of hydrogen peroxide using NCNT/NF/CNT air diffusion electrode for electro-Fenton degradation of p-nitrophenol. Water Sci Technol 73(7):1652–1658

    CAS  Google Scholar 

  • Wang L, Cao MH, Ai ZH, Zhang LZ (2015) Design of a highly efficient and wide pH electro-Fenton oxidation system with molecular oxygen activated by ferrous-tetrapolyphosphate complex. Environ Sci Technol 49(5):3032–3039

    CAS  Google Scholar 

  • Wang XC, Jie SS, Liu ZG (2019a) The influence of encapsulated cobalt content within N-doped bamboo-like carbon nanotubes catalysts for arylalkanes oxidation. Mater Chem Phys 232:393–399

    CAS  Google Scholar 

  • Wang DD, Li J, Xu ZF, Zhu YR, Chen GX (2019b) Preparation of novel flower-like BiVO4/Bi2Ti2O7/Fe3O4 for simultaneous removal of tetracycline and Cu2+: adsorption and photocatalytic mechanisms. J Colloid Interface Sci 533:344–357

    CAS  Google Scholar 

  • Wepasnick K, Smith B, Schrote K, Wilson H, Diegelmann S, Fairbrother D (2011) Surface and structural characterization of multi-walled carbon nanotubes following different oxidative treatments. Carbon 49(1):24–36

    CAS  Google Scholar 

  • Wu K, Jing CY, Zhang J, Liu T, Yang SJ, Wang WD (2019) Magnetic Fe3O4@CuO nanocomposite assembled on graphene oxide sheets for the enhanced removal of arsenic(III/V) from water. Appl Surf Sci 466:746–756

    CAS  Google Scholar 

  • Xia Y, Shang H, Zhang QG, Zhou YQ, Hu XH (2019) Electrogeneration of hydrogen peroxide using phosphorus-doped carbon nanotubes gas diffusion electrodes and its application in electro-Fenton. J Electroanal Chem 840:400–408

    CAS  Google Scholar 

  • Xie FC, Xu Y, Xia KY, Jia CX, Zhang P (2016) Alternate pulses of ultrasound and electricity enhanced electrochemical process for p-nitrophenol degradation. Ultrason Sonochem 28:199–206

    CAS  Google Scholar 

  • Xiong ZK, Lai B, Yuan Y, Cao JY, Yang P, Zhou YX (2016) Degradation of p-nitrophenol (PNP) in aqueous solution by a micro-size Fe0/O3 process (mFe0/O3): optimization, kinetic, performance and mechanism. Chem Eng J 302:137–145

    CAS  Google Scholar 

  • Xiong ZK, Zhang H, Zhang WC, Lai B, Yao G (2019) Removal of nitrophenols and their derivatives by chemical redox: a review. Chem Eng J 359:13–31

    CAS  Google Scholar 

  • Xu N, Zhang YY, Tao HC, Zhou SG, Zeng YQ (2013) Bio-electro-Fenton system for enhanced estrogens degradation. Bioresour Technol 138:136–140

    CAS  Google Scholar 

  • Xu WT, Chen JN, Qiu Y, Peng W, Shi N, Zhou JC (2019) Highly efficient microwave catalytic oxidation degradation of 4-nitrophenol over magnetically separable NiCo2O4-Bi2O2CO3 composite without adding oxidant. Sep Purif Technol 213:426–436

    CAS  Google Scholar 

  • Yang J, Pan B, Li H, Liao SH, Zhang D, Wu M, Xing BS (2016) Degradation of p-nitrophenol on biochars: role of persistent free radicals. Environ Sci Technol 50(2):694–700

    CAS  Google Scholar 

  • Yang YF, Ye J, Xu LD, Li H, Zhang Y, Wen JG, Wang HF (2018) Synergistic effect of TNSs-TiO2NPs/3DGNs catalysts on photocatalytic degradation of 4-nitrophenol under visible light. Appl Surf Sci 433:398–407

    CAS  Google Scholar 

  • Yao YJ, Chen H, Qin JC, Wu GD, Lian C, Zhang J, Wang SB (2016) Iron encapsulated in boron and nitrogen codoped carbon nanotubes as synergistic catalysts for Fenton-like reaction. Water Res 101:281–291

    CAS  Google Scholar 

  • Yao YJ, Lian C, Hu Y, Zhang J, Gao MX, Zhang Y, Wang SB (2017) Heteroatoms doped metal iron-polyvinylidene fluoride (PVDF) membrane for enhancing oxidation of organic contaminants. J Hazard Mater 338:265–275

    CAS  Google Scholar 

  • Zhang AL, Wang NN, Zhou JT, Jiang P, Liu GF (2012) Heterogeneous Fenton-like catalytic removal of p-nitrophenol in water using acid-activated fly ash. J Hazard Mater 201-202:68–73

    CAS  Google Scholar 

  • Zhang ZH, Meng HS, Wang YJ, Shi LM, Wang X, Chai SN (2018) Fabrication of graphene@graphite-based gas diffusion electrode for improving H2O2 generation in electro-Fenton process. Electrochim Acta 260:112–120

    CAS  Google Scholar 

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Funding

This research was financially supported by National Natural Science Foundation of China (No. 51708250) and the Science and Technology Project of Jilin Education Bureau (No. JJKH20180790KJ).

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Authors and Affiliations

  1. Key Laboratory of Environmental Materials and Pollution Control, The Education Department of Jilin Province, Jilin Normal University, Siping, 136000, China

    Qian Tang, Chunwei Yang & Yonghui Gao

  2. School of Environmental Science and Engineering, Jilin Normal University, Siping, 136000, China

    Qian Tang, Binglun Li, Wenge Ma, Hang Gao, Hao Zhou & Chunwei Yang

  3. School of Environmental Science and Technology, Dalian University of Technology, Dalian, 116024, China

    Dong Wang

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  1. Qian Tang
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  2. Binglun Li
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  4. Hang Gao
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  5. Hao Zhou
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  7. Yonghui Gao
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Correspondence to Qian Tang or Chunwei Yang.

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Tang, Q., Li, B., Ma, W. et al. Fabrication of a double-layer membrane cathode based on modified carbon nanotubes for the sequential electro-Fenton oxidation of p-nitrophenol. Environ Sci Pollut Res 27, 18773–18783 (2020). https://doi.org/10.1007/s11356-020-08364-5

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