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Fe/Cu Bimetallic Nanoparticles Highly Dispersed in MOF-Derived N-Doped Porous Carbon as Stable Heterogeneous Fenton Catalysts for Enrofloxacin Degradation

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Abstract

Metal–organic frameworks (MOFs) were used as precursors to prepare iron-based heterogeneous Fenton catalysts Fe@C, FeCu@C, and FeCu@N–C via pyrolysis. The catalytic activities were evaluated by measuring the decomposition rate of hydrogen peroxide (H2O2). The morphology, structure, and physical properties of the catalysts were analyzed through X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and nitrogen adsorption. The results showed that at 60 min, the decomposition rates of H2O2 by FeCu@C and FeCu@N–C were 95.4% and 92.5%, respectively, which were 18.5% and 15.6% higher than that by Fe@C, respectively. It was speculated that the iron and copper species present in the bimetallic nanoparticles were available active sites for the Fenton reaction. The synergistic effects between them can promote the activation and decomposition of H2O2. In addition, the nitrogen-doped catalysts FeCu@N–C had better pH applicability, better reusability, and lower iron leaching than FeCu@C. Nitrogen-doped carbon contributed to the enhanced catalytic performance. This can be attributed to the well dispersibility of Fe and Cu species on the N-doped carbon matrix. The FeCu@N–C was applied to the treatment of enrofloxacin (ENR) antibiotic wastewater. The results indicated that a 90% degradation rate can be achieved in 60 min under the initial concentration of ENR 20 mg/L, catalyst dosage 20 mg/L, H2O2 concentration 1.5 mM, the initial solution pH 3.60, 25 ℃. The rapid degradation of ENR was more relevant to the surface-bound ٠OH rather than free ٠OH and the heterogeneous Fenton reaction played the dominant role. This work provides a potential heterogeneous Fenton catalyst for antibiotics wastewater treatment.

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References

  1. Xie DH, Guo PC, Zhong KQ, Sheng GP (2022) Highly dispersed Co/Fe bimetal in carbonaceous cages as heterogeneous Fenton nanocatalysts for enhanced sulfamethoxazole degradation. Appl Catal B 319:121923. https://doi.org/10.1016/j.apcatb.2022.121923

    Article  CAS  Google Scholar 

  2. Ye JS, Liu J, Ou HS, Wang LL (2016) Degradation of ciprofloxacin by 280 nm ultraviolet-activated persulfate: Degradation pathway and intermediate impact on proteome of Escherichia coli. Chemosphere 165:311–319. https://doi.org/10.1016/j.chemosphere.2016.09.031

    Article  CAS  PubMed  Google Scholar 

  3. Guinea E, Garrido JA, Rodríguez RM, Cabot P, Arias C, Centellas F, Brillas E (2010) Degradation of the fluoroquinolone enrofloxacin by electrochemical advanced oxidation processes based on hydrogen peroxide electrogeneration. Electrochim Acta 55:2101–2115. https://doi.org/10.1016/j.electacta.2009.11.040

    Article  CAS  Google Scholar 

  4. Wang C, Yin L, Xu Z, Niu J, Hou LA (2017) Electrochemical degradation of enrofloxacin by lead dioxide anode: Kinetics, mechanism and toxicity evaluation. Chem Eng J 326:911–920. https://doi.org/10.1016/j.cej.2017.06.038

    Article  CAS  Google Scholar 

  5. Wang Q, Ma Y, Xing S (2018) Comparative study of Cu-based bimetallic oxides for Fenton-like degradation of organic pollutants. Chemosphere 203:450–456. https://doi.org/10.1016/j.chemosphere.2018.04.013

    Article  CAS  PubMed  Google Scholar 

  6. Zhang T, Ma QQ, Zhou MQ, Li C, Ai S (2021) Degradation of methylene blue by a heterogeneous Fenton reaction catalyzed by FeCo2O4-N-C nanocomposites derived by ZIFs. Powder Technol 383:212–219. https://doi.org/10.1016/j.powtec.2021.01.051

    Article  CAS  Google Scholar 

  7. Zhu JB, Xiao ML, Zhang YL, Jin Z, Peng ZQ, Liu CP, Chen SL, Ge JJ, Xing W (2016) Metal-organic framework-induced synthesis of ultra-small encased NiFe nanoparticles coupling with graphene as efficient oxygen electrode for rechargeable Zn-Air battery. ACS Catal 6:6335–6342. https://doi.org/10.1021/acscatal.6b01503

    Article  CAS  Google Scholar 

  8. Ting Yu, Chen H, Tong Hu, Feng J, Xing W, Tang L, Tang W (2024) Recent advances in the applications of encapsulated transition-metal nanoparticles in advanced oxidation processes for degradation of organic pollutants: A critical review. Appl Catal B 342:123401

    Article  Google Scholar 

  9. Kaneti YV, Tang J, Salunkhe RR, Jiang XC, Yu AB, Wu KC, Yamauchi Y (2017) Nanoarchitectured design of Porous materials and nanocomposites from Metal-organic Frameworks. Adv Mater 29(12):1604898.1-1604898.40. https://doi.org/10.1002/adma.201604898

    Article  CAS  Google Scholar 

  10. Chen YZ, Wang C, Wu ZY, Xiong YJ, Xu Q (2015) Metal-Organic Frameworks: From bimetallic Metal-organic Framework to porous carbon: High surface area and multicomponent active dopants for excellent electrocatalysis. Adv Mater 27(34):5010–5016. https://doi.org/10.1002/adma.201570229

    Article  CAS  PubMed  Google Scholar 

  11. Tang JT, Wang JL (2019) MOF-derived three-dimensional flower-like FeCu@C composite as an efficient Fenton-like catalyst for sulfamethazine degradation. Chem Eng J 375(122007):2019. https://doi.org/10.1016/j.cej.2019.122007

    Article  CAS  Google Scholar 

  12. Zhao HY, Chen Y, Peng QS, Wang QN, Zhao GH (2017) Catalytic activity of MOF(2Fe/Co)/carbon aerogel for improving H2O2 and (OH)-O-center dot generation in solar photo-electro-Fenton process. Appl Catal B-Environ 203:127–137. https://doi.org/10.1016/j.apcatb.2016.09.074

    Article  CAS  Google Scholar 

  13. Liu CW, Wang YP, Zhang YT, Li RY, Meng WD (2018) Enhancement of Fe@porous carbon to be an efficient mediator for peroxymonosulfate activation for oxidation of organic contaminants: Incorporation NH2-group into structure of its MOF precursor. Chem Eng J 354:835–848. https://doi.org/10.1016/j.cej.2018.08.060

    Article  CAS  Google Scholar 

  14. Enyu Liu,, Tong Hu, Naif Abdullah Al-Dhabi, Tseren-Ochir Soyol-Erdene, Ochirkhuyag Bayanjargal, Yuqi Zuo, Jiajia Wang, Wangwang Tang. MOF-derived Fe/Ni@C marigold-like nanosheets as heterogeneous electro-Fenton cathode for efficient antibiotic oxytetracycline degradation, Environmental Research 247 (2024) 118357

  15. Zhang J, Wang D, Zhao F, Feng J, Feng H, Luo J, Tang W (2022) Ferrate modified carbon felt as excellent heterogeneous electro-Fenton cathode for chloramphenicol degradation. Water Res 227:119324

    Article  CAS  PubMed  Google Scholar 

  16. Hu T, Deng FX, Feng HP, Zhang JJ, Shao BB, Feng CY, Tang WW, Tang L (2021) Fe/Co bimetallic nanoparticles embedded in MOF-derived nitrogen-doped porous carbon rods as efficient heterogeneous electro-Fenton catalysts for degradation of organic pollutants. Appl Mater Today 24:101161. https://doi.org/10.1016/j.apmt.2021.101161

    Article  Google Scholar 

  17. Ye Z, Padilla JA, Xuriguera E, Brillas E, Sirés I (2020) Magnetic MIL(Fe)-type MOF-derived N-doped nano-ZVI@C rods as heterogeneous catalyst for the electro-Fenton degradation of gemfibrozil in a complex aqueous matrix. Appl Catal B: Environ 266:118604. https://doi.org/10.1016/j.apcatb.2020.118604

    Article  CAS  Google Scholar 

  18. Xiao J, Wang C, Liu H (2020) Fenton-like degradation of dimethyl phthalate enhanced by quinone species. J Hazard Mat 382:121007. https://doi.org/10.1016/j.jhazmat.2019.121007

    Article  CAS  Google Scholar 

  19. Bokare AD, Choi W (2014) Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes. J Hazard Mater 275:121–135. https://doi.org/10.1016/j.jhazmat.2014.04.054

    Article  CAS  PubMed  Google Scholar 

  20. Pham AN, Xing GW, Miller CJ, Waite TD (2013) Fenton-like copper redox chemistry revisited: hydrogen peroxide and superoxide mediation of copper catalyzed oxidant production. J Catal 301:54–64. https://doi.org/10.1016/j.jcat.2013.01.025

    Article  CAS  Google Scholar 

  21. Tang JT, Wang JL (2020) Iron-copper bimetallic metal-organic frameworks for efficient Fentonlike degradation of sulfamethoxazole under mild conditions. Chemosphere 241:125002. https://doi.org/10.1016/j.chemosphere.2019.125002

    Article  CAS  PubMed  Google Scholar 

  22. Mai HD, Rafiq K, Yoo H (2017) Nano Metal-Organic Framework-Derived Inorganic Hybrid Nanomaterials: Synthetic Strategies and Applications. Chem-a Eur J 23(24):5631–5651. https://doi.org/10.1002/chem.201782461

    Article  CAS  Google Scholar 

  23. Jin WX, Ma SY, Tie ZZ, Wei JJ, Luo J, Jiang XH, Wang TT, Li WQ, Cheng L, Mao YZ (2015) One-step synthesis and highly gas-sensing properties of hierarchical Cu-doped SnO2 nanoflowers. Sens Actuators B-Chem 213:171–180. https://doi.org/10.1016/j.snb.2015.02.075

    Article  CAS  Google Scholar 

  24. Xiao J, Chen JW, Ou ZQ, Lai JH, Yu TW, Wang Y (2021) N-doped carbon-coated Fe3N composite as heterogeneous electro-Fenton catalyst for efficient degradation of organics. Chin J Catal 42:953–962. https://doi.org/10.1016/S1872-2067(20)63719-6

    Article  CAS  Google Scholar 

  25. Li TF, Li M, Zhang MR, Li X, Liu KH, Zhang MY, Liu X, Sun DM, Xu L, Zhang YW, Tang YW (2019) Immobilization of Fe3N nanoparticles within N-doped carbon nanosheet frameworks as a high-efficiency electrocatalyst for oxygen reduction reaction in Zn-air batteries. Carbon 153:364–371. https://doi.org/10.1016/j.carbon.2019.07.044

    Article  CAS  Google Scholar 

  26. Su P, Zhou MH, Lu XY, Yang WL, Ren GB, Cai JJ (2019) Electrochemical catalytic mechanism of N-doped graphene for enhanced H2O2 yield and in-situ degradation of organic pollutant. Appl Catal B-Environ 245:583–595. https://doi.org/10.1016/j.apcatb.2018.12.075

    Article  CAS  Google Scholar 

  27. Haider MR, Jiang WL, Han JL, Sharif HMA, Ding YC, Cheng HY, Wang AJ (2019) In-situ electrode fabrication from polyaniline derived N-doped carbon nanofibers for metal-free electro-Fenton degradation of organic contaminants. Appl Catal B 256:117774. https://doi.org/10.1016/j.apcatb.2019.117774

    Article  CAS  Google Scholar 

  28. Cao, P. K., Zhao, K., Quan, X., Chen, S., Yu, H.T., 2020. Efficient and stable heterogeneous electro-Fenton system using iron oxides embedded in Cu, N co-doped hollow porous carbon as functional electrocatalyst. Sep Purif Technol 238: https://doi.org/10.1016/j.seppur.2019.116424

  29. Pena-Mendez EM, Mawale RM, Conde-Gonzalez JE, Socas-Rodriguez B, Havel J, Ruiz-Perez C (2019) Metal organic framework composite, nano-Fe3O4@Fe-(benzene-1,3,5-tricarboxylic acid), for solid phase extraction of blood lipid regulators from water. Talanta 207:120275–120275. https://doi.org/10.1016/j.talanta.2019.120275

    Article  CAS  PubMed  Google Scholar 

  30. Li WH, Wu XF, Li SD, Tang WX, Chen YF (2018) Magnetic porous Fe3O4/carbon octahedra derived from iron-based metal-organic framework as heterogeneous Fenton-like catalyst. Appl Surf Sci 436:252–262. https://doi.org/10.1016/j.apsusc.2017.11.151

    Article  CAS  Google Scholar 

  31. Xu LJ, Wang JL (2012) Fenton-like degradation of 2,4-dichlorophenol using Fe3O4 magnetic nanoparticles. Appl Catal B Environ 123:117–126. https://doi.org/10.1016/j.apcatb.2012.04.028

    Article  CAS  Google Scholar 

  32. Wang JL, Xu LJ (2012) Advanced oxidation processes for wastewater treatment:formation of hydroxyl radical and application. Crit Rev Environ Sci Technol 42:251–325. https://doi.org/10.1080/10643389.2010.507698

    Article  CAS  Google Scholar 

  33. Xu LJ, Wang JL (2017) Magnetic nanoscaled Fe3O4/CeO2 composite as an efficient Fenton-like heterogeneous catalyst for degradation of 4-chlorophenol. Environ Sci Technol 46(18):10145–10153. https://doi.org/10.1021/es300303f

    Article  CAS  Google Scholar 

  34. Martin ST, Lee AT, Hoffmann MR (1995) Chemical mechanism of inorganic oxidants in the TiO2/UV process-increased rates of degradation of chlorinated hydrocarbons. Environ Sci Technol 29:2567–2573

    Article  CAS  PubMed  Google Scholar 

  35. Liu JL, Luo K, Li XM, Yang Q, Wang DB, Wu Y, Chen Z, Huang XD, Pi ZJ, Du WJ, Guan ZL (2020) The biochar-supported iron-copper bimetallic composite activating oxygen system for simultaneous adsorption and degradation of tetracycline. Chem Eng J 402:126039. https://doi.org/10.1016/j.cej.2020.126039

    Article  CAS  Google Scholar 

  36. Xia QX, Zhang DJ, Yao ZP, Jiang ZH (2022) Revealing the enhancing mechanisms of Fe-Cu bimetallic catalysts for the Fenton-like degradation of phenol. Chemosphere 289:133195. https://doi.org/10.1016/j.chemosphere.2021.133195

    Article  CAS  PubMed  Google Scholar 

  37. Tian YY, He XY, Zhou H, Tian XK, Nie YL, Zhou ZX, Yang C, Li Y (2020) Efficient Fenton-like degradation of ofloxacin over bimetallic Fe–Cu@Sepiolite composite. Chemosphere 257:127209. https://doi.org/10.1016/j.chemosphere.2020.127209

    Article  CAS  PubMed  Google Scholar 

  38. Yao Y, Chen H, Qin J, Wu G, Lian C, Zhang J, Wang S (2016) Iron encapsulated in boron and nitrogen codoped carbon nanotubes as synergistic catalysts for Fentonlike reaction. Water Res 101:281–291

    Article  CAS  PubMed  Google Scholar 

  39. Choi CH, Park SH, Woo SI (2012) Binary and ternary doping of nitrogen, boron, and phosphorus into carbon for enhancing electrochemical oxygen reduction activity. ACS Nano 6:7084–7091

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

The authors are grateful to the financial support of the National Natural Science Foundation of China (No.52374415, No.22078254, and No.62374130), the International Cooperation Program of Shaanxi Province (No.2024GH-ZDXM-25),  and the Natural Science Foundation of Shaanxi Province (No.2022JZ-29).

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Correspondence to Lihua Yu.

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Yu, L., Zhao, Y., Guo, S. et al. Fe/Cu Bimetallic Nanoparticles Highly Dispersed in MOF-Derived N-Doped Porous Carbon as Stable Heterogeneous Fenton Catalysts for Enrofloxacin Degradation. Catal Lett (2024). https://doi.org/10.1007/s10562-024-04654-6

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