Abstract
A columnar N-doped graphene aerogel (NGA) was successfully fabricated by one-step hydrothermal synthesis using L-hydroxyproline as reductant, N-doping, and swelling agent, and it was used as the cathode with internal aeration mode for the electro-Fenton degradation of p-nitrophenol. Owing to the stable solid–liquid–gas three-phase interface, more active defects, and modulated nitrogen dopants, the NGA cathode exhibited enhanced electrocatalytic activity. H2O2 could be continuously electro-generated via a two-electron oxygen reduction, and the yield of H2O2 was 153.3 mg·L−1·h−1 with the low electric energy consumption of 15.3 kWh kg−1. Simultaneously, the NGA cathode had better charge transfer capability with N-doping, which was conducive to the conversion of Fe3+/Fe2+. Under the optimal condition, nearly 100% removal of p-nitrophenol and 84% removal of TOC were obtained within 60 and 120 min, respectively. The NGA cathode also presented good stability and versatile applicability in different water matrices. Therefore, the NGA is a cost-effective cathode material in electro-Fenton system with adequate activity and reuse stabilization.
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References
Chen S, Tang L, Feng HP, Zhou YY, Zeng GM, Lu Y, Yu JF, Ren XY, Peng B, Liu XC (2019) Carbon felt cathodes for electro-Fenton process to remove tetracycline via synergistic adsorption and degradation. Sci Total Environ 670:921–931. https://doi.org/10.1016/j.scitotenv.2019.03.086
Deng FX, Li SX, Cao YL, Fang MA, Qu JH, Chen ZL, Qiu S (2020) A dual-cathode pulsed current electro-Fenton system: improvement for H2O2 accumulation and Fe3+ reduction. J Power Sources 466:228342. https://doi.org/10.1016/j.jpowsour.2020.228342
Dong CC, Ji JH, Shen B, Xing MY, Zhang JL (2018) Enhancement of H2O2 decomposition by the co-catalytic effect of WS2 on the Fenton reaction for the synchronous reduction of Cr(VI) and remediation of phenol. Environ Sci Technol 52(19):11297–11308. https://doi.org/10.1021/acs.est.8b02403
Dong P, Wang HL, Liu WJ, Wang SJ, Wang Y, Zhang JQ, Lin FF, Wang YQ, Zhao CC, Duan XG, Wang SB, Sun HQ (2021) Quasi-MOF derivative-based electrode for efficient electro-Fenton oxidation. J Hazard Mater 401:123423. https://doi.org/10.1016/j.jhazmat.2020.123423
Ganiyu SO, de Araújo MJG, Costa ECT, Santos JEL, dos Santos EV, Martínez-Huitle CA, Pergher SBC (2021) Design of highly efficient porous carbon foam cathode for electro-Fenton degradation of antimicrobial sulfanilamide. Appl Catal B-Environ 283:119652. https://doi.org/10.1016/j.apcatb.2020.119652
Guo MT, Lu MJ, Zhao H, Lin FF, He FT, Zhang JQ, Wang SJ, Dong P, Zhao CC (2022) Efficient electro-Fenton catalysis by self-supported CFP@CoFe2O4 electrode. J Hazard Mater 423:127033. https://doi.org/10.1016/j.jhazmat.2021.127033
He DQ, Zhang YJ, Pei DN, Huang GX, Liu C, Li J, Yu HQ (2020) Degradation of benzoic acid in an advanced oxidation process: the effects of reducing agents. J Hazard Mater 382:121090. https://doi.org/10.1016/j.jhazmat.2019.121090
Jiang YQ, Zhang JJ, Balasubramanian R (2022) Nitrogen-doped graphene aerogels with rational indium hydroxide decoration for highly efficient photocatalytic of p-nitrophenol. J Environ Chem Eng 10(1):107125. https://doi.org/10.1016/j.jece.2021.107125
Li HY, Xing X, Wang K, Zhu XP, Jiang Y, Xia JX (2018) Improved BDD anode system in electrochemical degradation of p-nitrophenol by corroding electrode of iron. Electrochim Acta 291:335–342. https://doi.org/10.1016/j.electacta.2018.09.128
Li XH, Liu F, Zhang WF, Lu HB, Zhang J (2019) Electrocatalytical oxidation of arsenite by reduced graphene oxide via in-situ electrocatalytic generation of H2O2. Environ Pollut 254:112958. https://doi.org/10.1016/j.envpol.2019.112958
Li D, Zheng T, Liu YL, Hou D, He HY, Song HR, Zhang JM, Tian SQ, Zhang W, Wang L, Ma J (2020a) A cost-effective electro-Fenton process with graphite felt electrode aeration for degradation of dimethyl phthalate: enhanced generation of H2O2 and iron recycling that simultaneously regenerates the electrode. Chem Eng J 394:125033. https://doi.org/10.1016/j.cej.2020.125033
Li X, Li C, Gao GY, Lv BS, Xu LS, Lu Y, Zhang GL (2020b) In-situ self-assembly of robust Fe (III)-carboxyl functionalized polyacrylonitrile polymeric bead catalyst for efficient photo-Fenton oxidation of p-nitrophenol. Sci Total Environ 702:134910. https://doi.org/10.1016/j.scitotenv.2019.134910
Li C, Hu CQ, Song Y, Sun YM, Yang WS, Ma M (2022) Graphene-based synthetic fabric cathodes with specific active oxygen functional groups for efficient hydrogen peroxide generation and homogeneous electro-Fenton processes. Carbon 186:699–710. https://doi.org/10.1016/j.carbon.2021.10.063
Liang JX, Zhang Y, Song CC, Tang DY, Sun J (2018) Double-potential electro-Fenton: a novel strategy coupling oxygen reduction reaction and Fe2+/Fe3+ recycling. Electrochem Commun 94:55–58. https://doi.org/10.1016/j.elecom.2018.08.006
Lima VN, Rodrigues CSD, Brandão YB, Benachour M, Madeira LM (2022) Optimisation of the degradation of 4-nitrophenol by Fenton’s process. J Water Process Eng 47:102685. https://doi.org/10.1016/j.jwpe.2022.102685
Liu XC, Li WQ, Wang YR, Zhou GN, Wang YX, He CS, Wang GM, Mu Y (2019) Cathode introduced atomic H* for Fe(II)-complex regeneration to effective electro-Fenton process at a natural pH. Environ Sci Technol 53(12):6927–6936. https://doi.org/10.1021/acs.est.9b00345
Liu MY, Feng ZY, Luan XM, Chu WH, Zhao HY, Zhao GH (2021) Accelerated Fe2+ regeneration in an effective electro-Fenton process by boosting internal electron transfer to a nitrogen conjugated Fe(III) complex. Environ Sci Technol 55(9):6042–6051. https://doi.org/10.1021/acs.est.0c08018
Luo ZP, Liu MT, Tang DY, Xu Y, Ran HH, He J, Chen K, Sun J (2022) High H2O2 selectivity and enhanced Fe2+ regeneration toward an effective electro-Fenton process based on a self-doped porous biochar cathode. Appl Catal B-Environ 315:121523. https://doi.org/10.1016/j.apcatb.2022.121523
Meijide J, Pazos M, Sanromán MÁ (2019) Heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride degradation. Environ Sci Pollut Res 26:3145–3156. https://doi.org/10.1007/s11356-017-0403-6
Niu XL, Li XY, Chen W, Li XB, Weng WJ, Yin CX, Dong RX, Sun W, Li GJ (2018) Three-dimensional reduced graphene oxide aerogel modified electrode for the sensitive quercetin sensing and its application. Mater Sci Eng C 89:230–236. https://doi.org/10.1016/j.msec.2018.04.015
Oturan N, Bo J, Trellu C, Oturan MA (2021) Comparative performance of ten electrodes in electro-Fenton process for removal of organic pollutants from water. ChemElectroChem 8(17):3294–3303. https://doi.org/10.1002/celc.202100588
Qi HQ, Sun XP, Sun ZR (2021a) Porous graphite felt electrode with catalytic defects for enhanced degradation of pollutants by electro-Fenton process. Chem Eng J 403:126270. https://doi.org/10.1016/j.cej.2020.126270
Qi LH, Jiang HL, Lin TN, Chang XY, Jiang BL (2021b) Fabrication of MIL-53(Al) based composites from biomass activated carbon (AC) for efficient p-nitrophenol adsorption from aqueous solution. J Taiwan Inst Chem E 127:220–227. https://doi.org/10.1016/j.jtice.2021.08.020
Qin YX, Song FH, Ai ZH, Zhang PP, Zhang LZ (2015) Protocatechuic acid promoted alachlor degradation in Fe(III)/H2O2 Fenton system. Environ Sci Technol 49(13):7948–7956. https://doi.org/10.1021/es506110w
Ren XH, Guo HH, Feng JK, Si PC, Zhang L, Ci LJ (2018) Synergic mechanism of adsorption and metal-free catalysis for phenol degradation by N-doped graphene aerogel. Chemosphere 191:389–399. https://doi.org/10.1016/j.chemosphere.2017.10.076
Rodrigues CSD, Borges RAC, Lima VN, Madeira LM (2018) p-Nitrophenol degradation by Fenton’s oxidation in a bubble column reactor. J Environ Manage 206:774–785. https://doi.org/10.1016/j.jenvman.2017.11.032
Salmerón I, Oller I, Plakas KV, Malato S (2021) Carbon-based cathodes degradation during electro-Fenton treatment at pilot scale: changes in H2O2 electrogeneration. Chemosphere 275:129962. https://doi.org/10.1016/j.chemosphere.2021.129962
Shi YC, Feng JJ, Lin XX, Zhang L, Yuan JH, Zhang QL, Wang AJ (2019) One-step hydrothermal synthesis of three-dimensional nitrogen-doped reduced graphene oxide hydrogels anchored PtPd alloyed nanoparticles for ethylene glycol oxidation and hydrogen evolution reactions. Electrochim Acta 293:504–513. https://doi.org/10.1016/j.electacta.2018.10.068
Sopaj F, Oturan N, Pinson J, Podvorica FI, Oturan MA (2020) Effect of cathode material on electro-Fenton process efficiency for electrocatalytic mineralization of the antibiotic sulfamethazine. Chem Eng J 384:123249. https://doi.org/10.1016/j.cej.2019.123249
Sun C, Chen T, Huang QX, Duan XG, Zhan MX, Ji LJ, Li XD, Wang SB, Yan JH (2021) Biochar cathode: reinforcing electro-Fenton pathway against four-electron reduction by controlled carbonization and surface chemistry. Sci Total Environ 754:142136. https://doi.org/10.1016/j.scitotenv.2020.142136
Tian M, Zhu YZ, Zhang DL, Wang M, Chen Y, Yang YJ, Gao SY (2019) Pyrrolic-nitrogen rich biomass-derived catalyst for sustainable degradation of organic pollutant via a self-powered electro-Fenton process. Nano Energy 64:103940. https://doi.org/10.1016/j.nanoen.2019.103940
Wang CJ, Shen J, Chen RG, Cao F, Jin B (2020) Self-assembled BiOCl/Ti3C2Tx composites with efficient photo-induced charge separation activity for photocatalytic degradation of p-nitrophenol. Appl Surf Sci 519:146175. https://doi.org/10.1016/j.apsusc.2020.146175
Wang YJ, Chen J, Gao JX, Meng HS, Chai SN, Jian YF, Shi LM, Wang YB, He C (2021) Selective electrochemical H2O2 generation on the graphene aerogel for efficient electro-Fenton degradation of ciprofloxacin. Sep Purif Technol 272:118884. https://doi.org/10.1016/j.seppur.2021.118884
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. https://doi.org/10.1016/j.jelechem.2019.04.009
Xing LY, Wei J, Liu XH, Zhang YF, Xu MD, Li JM, Pan GP, Li J (2022) Application of energy sustainable utilization strategy for highly efficient electro-Fenton treatment of antibiotics. J Environ Chem Eng 10:107059. https://doi.org/10.1016/j.jece.2021.107059
Xu H, Guo HK, Chai CS, Li N, Lin XY, Xu WJ (2022) Anodized graphite felt as an efficient cathode for in-situ hydrogen peroxide production and electro-Fenton degradation of rhodamine B. Chemosphere 286:131936. https://doi.org/10.1016/j.chemosphere.2021.131936
Yang WL, Zhou MH, Liang L (2018) 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
Yang YQ, Gu YX, Lin HD, Jie BR, Zheng ZH, Zhang XD (2022) Bicarbonate-enhanced iron-based Prussian blue analogs catalyze the Fenton-like degradation of p-nitrophenol. J Colloid Interf Sci 608:2884–2895. https://doi.org/10.1016/j.jcis.2021.11.015
Ye ZH, Brillas E, Centellas F, Cabot PL, Sirés I (2019) Electro-Fenton process at mild pH using Fe(III)-EDDS as soluble catalyst and carbon felt as cathode. Appl Catal B-Environ 257:117907. https://doi.org/10.1016/j.apcatb.2019.117907
You HJ, Chen Z, Yu Q, Zhu W, Chen BY, Lv Z, Hu Q, Liu YY, Zheng ZY, Li ST, Yeasmin F (2021) Preparation of a three-dimensional porous PbO2-CNTs composite electrode and study of the degradation behavior of p-nitrophenol. Sep Purif Technol 276:119406. https://doi.org/10.1016/j.seppur.2021.119406
Yu FK, Wang Y, Ma HR, Zhou MH (2020) Hydrothermal synthesis of FeS2 as a highly efficient heterogeneous electro-Fenton catalyst to degrade diclofenac via molecular oxygen effects for Fe(II)/Fe(III) cycle. Sep Purif Technol 248:117022. https://doi.org/10.1016/j.seppur.2020.117022
Zhang DY, Liu TC, Yin K, Liu CB, Wei YF (2020a) Selective H2O2 production on N-doped porous carbon from direct carbonization of metal organic frameworks for electro-Fenton mineralization of antibiotics. Chem Eng J 383:123184. https://doi.org/10.1016/j.cej.2019.123184
Zhang QZ, Zhou MH, Ren GB, Li YW, Li YC, Du XD (2020b) Highly efficient electrosynthesis of hydrogen peroxide on a superhydrophobic three-phase interface by natural air diffusion. Nat Commun 11(1):1731. https://doi.org/10.1038/s41467-020-15597-y
Zhang QZ, Zhou MH, Du XD, Su P, Fu WY, Song G (2022a) Highly efficient dual-cathode electro-Fenton process without aeration at a wide pH range: Simultaneously enhancing Fe(II) regeneration and mineralization efficiency. Chem Eng J 429:132436. https://doi.org/10.1016/j.cej.2021.132436
Zhang T, Wu JD, Wang Z, Wei Z, Liu JH, Gong XZ (2022b) Transfer of molecular oxygen and electrons improved by the regulation of C-N/C=O for highly efficient 2e-ORR. Chem Eng J 433:133591. https://doi.org/10.1016/j.cej.2021.133591
Zhao XR, Xu X, Teng J, Zhou N, Zhou Z, Jiang XY, Jiao FP, Yu JG (2019) Three-dimensional porous graphene oxide-maize amylopectin composites with controllable pore-sizes and good adsorption-desorption properties: facile fabrication and reutilization, and the adsorption mechanism. Ecotox Environ Safe 176:11–19. https://doi.org/10.1016/j.ecoenv.2019.03.069
Zhou HJ, Dong HC, Wang JH, Chen YC (2021) Cobalt anchored on porous N, P, S-doping core-shell with generating/activating dual reaction sites in heterogeneous electro-Fenton process. Chem Eng J 406:125990. https://doi.org/10.1016/j.cej.2020.125990
Zhu YS, Qiu S, Deng FX, Ma F, Zheng YS (2020) Degradation of sulfathiazole by electro-Fenton using a nitrogen-doped cathode and a BDD anode: insight into the H2O2 generation and radical oxidation. Sci Total Environ 722:137853. https://doi.org/10.1016/j.scitotenv.2020.137853
Zhu YS, Deng FX, Qiu S, Ma F, Zheng YS, Lian RQ (2021) Enhanced electro-Fenton degradation of sulfonamides using the N, S co-doped cathode: mechanism for H2O2 formation and pollutants decay. J Hazard Mater 403:123950. https://doi.org/10.1016/j.jhazmat.2020.123950
Zuo C, Li LF, Chen WQ, Zhang Z (2021) Synergistic effect on the four-electron ORR of the electro-Fenton system to remove micropollutants using an MOF-derived catalyst with carbon black. Appl Surf Sci 554:149546. https://doi.org/10.1016/j.apsusc.2021.149546
Funding
This research was financially supported by National Natural Science Foundation of China (No. 51708250), Natural Science Foundation of Jilin Province (No. 20210101391JC), and Scientific research project of Education Department of Jilin Province (No. JJKH20220451KJ).
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QT: conceptualization, methodology, funding acquisition, writing, review, and editing. SL: investigation, experiment, data analysis, and writing. HG: investigation, experiment, data analysis, and writing. YF: investigation, formal analysis, and writing. WB: data analysis and writing. YG: methodology and investigation. YS: funding acquisition, review, and editing. CY: formal analysis, review, and editing.
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Tang, Q., Luo, S., Gao, H. et al. N-doped graphene aerogel cathode with internal aeration for enhanced degradation of p-nitrophenol by electro-Fenton process. Environ Sci Pollut Res 30, 23481–23493 (2023). https://doi.org/10.1007/s11356-022-23868-y
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DOI: https://doi.org/10.1007/s11356-022-23868-y