Abstract
Hydrogen peroxide (H2O2) electrogenerated via two-electron oxygen reduction reaction at cathode plays an important role in electrochemical advanced oxidation processes for organic pollutants removal from wastewater. Herein, multi-walled carbon nanotubes and carbon black co-modified graphite felt electrode (MWCNTs-CB/GF) was prepared as an efficient cathode for H2O2 electrogeneration and amoxicillin removal by anodic oxidation with hydrogen peroxide (AO-H2O2) and electro-Fenton (EF) under mild pH condition. Besides, the physicochemical and electrochemical properties of MWCNTs-CB/GF were characterized by scanning electron microscopy, N2 adsorption and desorption experiment, contact angle measurement, X-ray photoelectron spectroscopy, and linear sweep voltammetry. Compared with GF, MWCNTs-CB/GF showed a higher H2O2 generation of 309.0 mg L−1 with a current efficiency of 60.9% (after 120 min) and more effective amoxicillin removal efficiencies of 97.5% (after 120 min) and 98.7% (after 30 min) in AO-H2O2 and EF (with 0.5 mM Fe2+) processes, under the condition of current density 12 mA cm−2 and initial pH 5.5. Meanwhile, the TOC removal efficiency was 45.2% during EF process after 120 min. Anodic oxidation, H2O2 oxidation, and methanol capture indicated that ∙OH generated via electro-activation reaction at MWCNTs-CB/GF and Fenton reaction in solution played the dominant role in amoxicillin removal. Moreover, the TOC removal was associated with ∙OH generated during Fenton reaction in the solution. The major intermediates of AMX degradation by EF process were identified using LC-MS and the possible degradation pathways were proposed containing of β-lactam ring opening, hydroxylation reaction, decarboxylation reaction, methyl groups in the thiazolidine ring oxidation reaction, bond cleavage, and rearrangement processes. All of the above results proved that MWCNTs-CB/GF was an excellent cathode for AMX degradation under mild pH condition.
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References
Andreozzi R, Canterino M, Marotta R, Paxeus N (2005) Antibiotic removal from wastewaters: the ozonation of amoxicillin. J Hazard Mater 122:243–250. https://doi.org/10.1016/j.jhazmat.2005.03.004
Ayodele OB, Lim JK, Hameed BH (2012) Pillared montmorillonite supported ferric oxalate as heterogeneous photo-Fenton catalyst for degradation of amoxicillin. Appl Catal A-Gen 413-414:301–309. https://doi.org/10.1016/j.apcata.2011.11.023
Babaei-Sati R, Basiri Parsa J (2017) Electrogeneration of H2O2 using graphite cathode modified with electrochemically synthesized polypyrrole/MWCNT nanocomposite for electro-Fenton process. J Ind Eng Chem 52:270–276. https://doi.org/10.1016/j.jiec.2017.03.056
Berenguer R, Nishihara H, Itoi H, Ishii T, Morallón E, Cazorla-Amorós D, Kyotani T (2013) Electrochemical generation of oxygen-containing groups in an ordered microporous zeolite-templated carbon. Carbon 54:94–104. https://doi.org/10.1016/j.carbon.2012.11.007
Bergamonti L, Bergonzi C, Graiff C, Lottici PP, Bettini R, Elviri L (2019) 3D printed chitosan scaffolds: a new TiO2 support for the photocatalytic degradation of amoxicillin in water. Water Res 163:114841. https://doi.org/10.1016/j.watres.2019.07.008
Brillas E, Sires I, Oturan MA (2009) Electro-Fenton process and related electrochemical technologies based on Fenton’s reaction chemistry. Chem Rev 109:6570–6631. https://doi.org/10.1021/cr900136g
Campos-Martin JM, Blanco-Brieva G, Fierro JL (2006) Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process. Angew Chem-Int Edit 45:6962–6984. https://doi.org/10.1002/anie.200503779
Carvalho IT, Santos L (2016) Antibiotics in the aquatic environments: a review of the European scenario. Environ Int 94:736–757. https://doi.org/10.1016/j.envint.2016.06.025
Chang C, Fu Y, Hu M, Wang C, Shan G, Zhu L (2013) Photodegradation of bisphenol A by highly stable palladium-doped mesoporous graphite carbon nitride (Pd/mpg-C3N4) under simulated solar light irradiation. Appl Catal B-Environ 142-143:553–560. https://doi.org/10.1016/j.apcatb.2013.05.044
Coria G, Pérez T, Sirés I, Nava JL (2015) Mass transport studies during dissolved oxygen reduction to hydrogen peroxide in a filter-press electrolyzer using graphite felt, reticulated vitreous carbon and boron-doped diamond as cathodes. J Electroanal Chem 757:225–229. https://doi.org/10.1016/j.jelechem.2015.09.031
Dong H, Su H, Chen Z, Yu H, Yu H (2016) Fabrication of electrochemically reduced graphene oxide modified gas diffusion electrode for in-situ electrochemical advanced oxidation process under mild conditions. Electrochim Acta 222:1501–1509. https://doi.org/10.1016/j.electacta.2016.11.131
Flores N, Sirés I, Rodríguez RM, Centellas F, Cabot PL, Garrido JA, Brillas E (2017) Removal of 4-hydroxyphenylacetic acid from aqueous medium by electrochemical oxidation with a BDD anode: mineralization, kinetics and oxidation products. J Electroanal Chem 793:58–65. https://doi.org/10.1016/j.jelechem.2016.07.042
Frontistis Z, Antonopoulou M, Venieri D, Konstantinou I, Mantzavinos D (2017) Boron-doped diamond oxidation of amoxicillin pharmaceutical formulation: statistical evaluation of operating parameters, reaction pathways and antibacterial activity. J Environ Manag 195:100–109. https://doi.org/10.1016/j.jenvman.2016.04.035
Ganiyu SO, Vieira Dos Santos E, Tossi de Araujo Costa EC, Martinez-Huitle CA (2018) Electrochemical advanced oxidation processes (EAOPs) as alternative treatment techniques for carwash wastewater reclamation. Chemosphere 211:998–1006. https://doi.org/10.1016/j.chemosphere.2018.08.044
Garza-Campos B, Morales-Acosta D, Hernández-Ramírez A, Guzmán-Mar JL, Hinojosa-Reyes L, Manríquez J, Ruiz-Ruiz EJ (2018) Air diffusion electrodes based on synthetized mesoporous carbon for application in amoxicillin degradation by electro-Fenton and solar photo electro-Fenton. Electrochim Acta 269:232–240. https://doi.org/10.1016/j.electacta.2018.02.139
Guo W, Wu QL, Zhou XJ, Cao HO, Du JS, Yin RL, Ren NQ (2015) Enhanced amoxicillin treatment using the electro-peroxone process: key factors and degradation mechanism. RSC Adv 5:52695–52702. https://doi.org/10.1039/c5ra07951a
He H, Jiang B, Yuan J, Liu Y, Bi X, Xin S (2019) Cost-effective electrogeneration of H2O2 utilizing HNO3 modified graphite/polytetrafluoroethylene cathode with exterior hydrophobic film. J Colloid Interface Sci 533:471–480. https://doi.org/10.1016/j.jcis.2018.08.092
Heuer H, Schmitt H, Smalla K (2011) Antibiotic resistance gene spread due to manure application on agricultural fields. Curr Opin Microbiol 14:236–243. https://doi.org/10.1016/j.mib.2011.04.009
Homem V, Alves A, Santos L (2010) Amoxicillin degradation at ppb levels by Fenton’s oxidation using design of experiments. Sci Total Environ 408:6272–6280. https://doi.org/10.1016/j.scitotenv.2010.08.058
Ji JY, Xing YJ, Ma ZT, Cai J, Zheng P, Lu HF (2013) Toxicity assessment of anaerobic digestion intermediates and antibiotics in pharmaceutical wastewater by luminescent bacterium. J Hazard Mater 246-247:319–323. https://doi.org/10.1016/j.jhazmat.2012.12.025
Jiang HR, Shyy W, Wu MC, Zhang RH, Zhao TS (2019) A bi-porous graphite felt electrode with enhanced surface area and catalytic activity for vanadium redox flow batteries. Appl Energy 233-234:105–113. https://doi.org/10.1016/j.apenergy.2018.10.033
Jung YJ, Kim WG, Yoon Y, Kang JW, Hong YM, Kim HW (2012) Removal of amoxicillin by UV and UV/H2O2 processes. Sci Total Environ 420:160–167. https://doi.org/10.1016/j.scitotenv.2011.12.011
Kaur R, Kushwaha JP, Singh N (2019a) Amoxicillin electro-catalytic oxidation using Ti/RuO2 anode: mechanism, oxidation products and degradation pathway. Electrochim Acta 296:856–866. https://doi.org/10.1016/j.electacta.2018.11.114
Kaur R, Kushwaha JP, Singh N (2019b) Electro-oxidation of amoxicillin trihydrate in continuous reactor by Ti/RuO2 anode. Sci Total Environ 677:84–97. https://doi.org/10.1016/j.scitotenv.2019.04.339
Kerkez-Kuyumcu Ö, Bayazit ŞS, Salam MA (2016) Antibiotic amoxicillin removal from aqueous solution using magnetically modified graphene nanoplatelets. J Ind Eng Chem 36:198–205. https://doi.org/10.1016/j.jiec.2016.01.040
Klauson D, Babkina J, Stepanova K, Krichevskaya M, Preis S (2010) Aqueous photocatalytic oxidation of amoxicillin. Catal Today 151:39–45. https://doi.org/10.1016/j.cattod.2010.01.015
Klein EY, Van Boeckel TP, Martinez EM et al (2018) Global increase and geographic convergence in antibiotic consumption between 2000 and 2015. Proc Natl Acad Sci U S A 115:E3463–E3470. https://doi.org/10.1073/pnas.1717295115
Kummerer K (2009) Antibiotics in the aquatic environment—a review—part I. Chemosphere 75:417–434. https://doi.org/10.1016/j.chemosphere.2008.11.086
Lei H, Li H, Li Z, Li Z, Chen K, Zhang X, Wang H (2010) Electro-Fenton degradation of cationic red X-GRL using an activated carbon fiber cathode. Process Saf Environ Prot 88:431–438. https://doi.org/10.1016/j.psep.2010.06.005
Li M, Zeng Z, Li Y, Arowo M, Chen J, Meng H, Shao L (2015) Treatment of amoxicillin by O3/Fenton process in a rotating packed bed. J Environ Manag 150:404–411. https://doi.org/10.1016/j.jenvman.2014.12.019
Liang L, Yu F, An Y, Liu M, Zhou M (2017) Preparation of transition metal composite graphite felt cathode for efficient heterogeneous electro-Fenton process. Environ Sci Pollut Res 24:1122–1132. https://doi.org/10.1007/s11356-016-7389-3
Luo H, Li C, Wu C, Zheng W, Dong X (2015) Electrochemical degradation of phenol by in situ electro-generated and electro-activated hydrogen peroxide using an improved gas diffusion cathode. Electrochim Acta 186:486–493. https://doi.org/10.1016/j.electacta.2015.10.194
Ma P, Ma H, Galia A, Sabatino S, Scialdone O (2019) Reduction of oxygen to H2O2 at carbon felt cathode in undivided cells. Effect of the ratio between the anode and the cathode surfaces and of other operative parameters. Sep Purif Technol 208:116–122. https://doi.org/10.1016/j.seppur.2018.04.062
Meng LW, Xk L, Wang K, Ma KL, Zhang J (2015) Influence of the amoxicillin concentration on organics removal and microbial community structure in an anaerobic EGSB reactor treating with antibiotic wastewater. Chem Eng J 274:94–101. https://doi.org/10.1016/j.cej.2015.03.065
Mi X, Li Y, Ning X et al (2019) Electro-Fenton degradation of ciprofloxacin with highly ordered mesoporous MnCo2O4-CF cathode: enhanced redox capacity and accelerated electron transfer. Chem Eng J 358:299–309. https://doi.org/10.1016/j.cej.2018.10.047
Michael I, Rizzo L, McArdell CS et al (2013) Urban wastewater treatment plants as hotspots for the release of antibiotics in the environment: a review. Water Res 47:957–995. https://doi.org/10.1016/j.watres.2012.11.027
Moreira FC, Boaventura RAR, Brillas E, Vilar VJP (2017) Electrochemical advanced oxidation processes: a review on their application to synthetic and real wastewaters. Appl Catal B-Environ 202:217–261. https://doi.org/10.1016/j.apcatb.2016.08.037
Mutiyar PK, Mittal AK (2014) Occurrences and fate of selected human antibiotics in influents and effluents of sewage treatment plant and effluent-receiving river Yamuna in Delhi (India). Environ Monit Assess 186:541–557. https://doi.org/10.1007/s10661-013-3398-6
Oturan N, Ganiyu SO, Raffy S, Oturan MA (2017) Sub-stoichiometric titanium oxide as a new anode material for electro-Fenton process: application to electrocatalytic destruction of antibiotic amoxicillin. Appl Catal B-Environ 217:214–223. https://doi.org/10.1016/j.apcatb.2017.05.062
Padilla-Robles BG, Alonso A, Martínez-Delgadillo SA, González-Brambila M, Jaúregui-Haza UJ, Ramírez-Muñoz J (2015) Electrochemical degradation of amoxicillin in aqueous media. Chem Eng Process 94:93–98. https://doi.org/10.1016/j.cep.2014.12.007
Pajootan E, Arami M, Rahimdokht M (2014) Discoloration of wastewater in a continuous electro-Fenton process using modified graphite electrode with multi-walled carbon nanotubes/surfactant. Sep Purif Technol 130:34–44. https://doi.org/10.1016/j.seppur.2014.04.025
Pan Z, Wang K, Wang Y, Tsiakaras P, Song S (2018) In-situ electrosynthesis of hydrogen peroxide and wastewater treatment application: a novel strategy for graphite felt activation. Appl Catal B-Environ 237:392–400. https://doi.org/10.1016/j.apcatb.2018.05.079
Panizza M, Dirany A, Sirés I, Haidar M, Oturan N, Oturan MA (2014) Complete mineralization of the antibiotic amoxicillin by electro-Fenton with a BDD anode. J Appl Electrochem 44:1327–1335. https://doi.org/10.1007/s10800-014-0740-9
Panizza M, Oturan MA (2011) Degradation of Alizarin Red by electro-Fenton process using a graphite-felt cathode. Electrochim Acta 56:7084–7087. https://doi.org/10.1016/j.electacta.2011.05.105
Petrie B, Barden R, Kasprzyk-Hordern B (2015) A review on emerging contaminants in wastewaters and the environment: current knowledge, understudied areas and recommendations for future monitoring. Water Res 72:3–27. https://doi.org/10.1016/j.watres.2014.08.053
Pipi AR, Sires I, De Andrade AR, Brillas E (2014) Application of electrochemical advanced oxidation processes to the mineralization of the herbicide diuron. Chemosphere 109:49–55. https://doi.org/10.1016/j.chemosphere.2014.03.006
Plakas KV, Karabelas AJ, Sklari SD, Zaspalis VT (2013) Toward the development of a novel electro-Fenton system for eliminating toxic organic substances from water. Part 1. In situ generation of hydrogen peroxide. Ind Eng Chem Res 52:13948–13956. https://doi.org/10.1021/ie400613k
Sheng Y, Zhao Y, Wang X, Wang R, Tang T (2014) Electrogeneration of H2O2 on a composite acetylene black–PTFE cathode consisting of a sheet active core and a dampproof coating. Electrochim Acta 133:414–421. https://doi.org/10.1016/j.electacta.2014.04.071
Sopaj F, Rodrigo MA, Oturan N, Podvorica FI, Pinson J, Oturan MA (2015) Influence of the anode materials on the electrochemical oxidation efficiency. Application to oxidative degradation of the pharmaceutical amoxicillin. Chem Eng J 262:286–294. https://doi.org/10.1016/j.cej.2014.09.100
Theofanidis SA, Batchu R, Galvita VV, Poelman H, Marin GB (2016) Carbon gasification from Fe–Ni catalysts after methane dry reforming. Appl Catal B-Environ 185:42–55. https://doi.org/10.1016/j.apcatb.2015.12.006
Tian J, Olajuyin AM, Mu T, Yang M, Xing J (2016) Efficient degradation of rhodamine B using modified graphite felt gas diffusion electrode by electro-Fenton process. Environ Sci Pollut Res 23:11574–11583. https://doi.org/10.1007/s11356-016-6360-7
Trovo AG, Nogueira RF, Aguera A, Fernandez-Alba AR, Malato S (2011) Degradation of the antibiotic amoxicillin by photo-Fenton process—chemical and toxicological assessment. Water Res 45:1394–1402. https://doi.org/10.1016/j.watres.2010.10.029
Wang H, Sun DZ, Bian ZY (2010) Degradation mechanism of diethyl phthalate with electrogenerated hydroxyl radical on a Pd/C gas-diffusion electrode. J Hazard Mater 180:710–715. https://doi.org/10.1016/j.jhazmat.2010.04.095
Wang J, Ben W, Yang M, Zhang Y, Qiang Z (2016) Dissemination of veterinary antibiotics and corresponding resistance genes from a concentrated swine feedlot along the waste treatment paths. Environ Int 92-93:317–323. https://doi.org/10.1016/j.envint.2016.04.020
Wang Y, Liu Y, Wang K, Song S, Tsiakaras P, Liu H (2015) Preparation and characterization of a novel KOH activated graphite felt cathode for the electro-Fenton process. Appl Catal B-Environ 165:360–368. https://doi.org/10.1016/j.apcatb.2014.09.074
Wang Y, Zhou W, Gao J, Ding Y, Kou K (2019) Oxidative modification of graphite felts for efficient H2O2 electrogeneration: enhancement mechanism and long-term stability. J Electroanal Chem 833:258–268. https://doi.org/10.1016/j.jelechem.2018.11.051
Yang H, Zhou M, Yang W, Ren G, Ma L (2018a) Rolling-made gas diffusion electrode with carbon nanotube for electro-Fenton degradation of acetylsalicylic acid. Chemosphere 206:439–446. https://doi.org/10.1016/j.chemosphere.2018.05.027
Yang W, Zhou M, Cai J, Liang L, Ren G, Jiang L (2017) Ultrahigh yield of hydrogen peroxide on graphite felt cathode modified with electrochemically exfoliated graphene. J Mater Chem A 5:8070–8080. https://doi.org/10.1039/c7ta01534h
Yang W, Zhou M, Liang L (2018b) Highly efficient in-situ metal-free electrochemical advanced oxidation process using graphite felt modified with N-doped graphene. Chem Eng J 338:700–708. https://doi.org/10.1016/j.cej.2018.01.013
Yu F, Chen Y, Ma H (2018) Ultrahigh yield of hydrogen peroxide and effective diclofenac degradation on a graphite felt cathode loaded with CNTs and carbon black: an electro-generation mechanism and a degradation pathway. New J Chem 42:4485–4494. https://doi.org/10.1039/c7nj04925k
Yu F, Zhou M, Yu X (2015) Cost-effective electro-Fenton using modified graphite felt that dramatically enhanced on H2O2 electro-generation without external aeration. Electrochim Acta 163:182–189. https://doi.org/10.1016/j.electacta.2015.02.166
Zha S, Cheng Y, Gao Y, Chen Z, Megharaj M, Naidu R (2014) Nanoscale zero-valent iron as a catalyst for heterogeneous Fenton oxidation of amoxicillin. Chem Eng J 255:141–148. https://doi.org/10.1016/j.cej.2014.06.057
Zhang Y, Xiao Y, Zhong Y, Lim T-T (2019) Comparison of amoxicillin photodegradation in the UV/H2O2 and UV/persulfate systems: reaction kinetics, degradation pathways, and antibacterial activity. Chem Eng J 372:420–428. https://doi.org/10.1016/j.cej.2019.04.160
Zhang Z, Meng H, Wang Y, Shi L, Wang X, Chai S (2018) Fabrication of graphene@graphite-based gas diffusion electrode for improving H2O2 generation in electro-Fenton process. Electrochim Acta 260:112–120. https://doi.org/10.1016/j.electacta.2017.11.048
Zhao H, Qian L, Chen Y, Wang Q, Zhao G (2018) Selective catalytic two-electron O2 reduction for onsite efficient oxidation reaction in heterogeneous electro-Fenton process. Chem Eng J 332:486–498. https://doi.org/10.1016/j.cej.2017.09.093
Zhou L, Zhou M, Hu Z, Bi Z, Serrano KG (2014) Chemically modified graphite felt as an efficient cathode in electro-Fenton for p-nitrophenol degradation. Electrochim Acta 140:376–383. https://doi.org/10.1016/j.electacta.2014.04.090
Zhou L, Zhou M, Zhang C, Jiang Y, Bi Z, Yang J (2013) Electro-Fenton degradation of p-nitrophenol using the anodized graphite felts. Chem Eng J 233:185–192. https://doi.org/10.1016/j.cej.2013.08.044
Zhou M, Yu Q, Lei L, Barton G (2007) Electro-Fenton method for the removal of methyl red in an efficient electrochemical system. Sep Purif Technol 57:380–387. https://doi.org/10.1016/j.seppur.2007.04.021
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This work was supported by National Natural Science Foundation of China (51778013) and Beijing Natural Science Foundation (8192005).
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Pan, G., Sun, X. & Sun, Z. Fabrication of multi-walled carbon nanotubes and carbon black co-modified graphite felt cathode for amoxicillin removal by electrochemical advanced oxidation processes under mild pH condition. Environ Sci Pollut Res 27, 8231–8247 (2020). https://doi.org/10.1007/s11356-019-07358-2
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DOI: https://doi.org/10.1007/s11356-019-07358-2