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Fe3O4@Cu/C and Fe3O4@CuO Composites Derived from Magnetic Metal–Organic Frameworks Fe3O4@HKUST-1 with Improved Peroxidase-Like Catalytic Activity

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Fe3O4@Cu/C and Fe3O4@CuO composites were achieved using nanoparticle-encapsulated MOFs Fe3O4@HKUST-1 as both a precursor and a self-sacrificing template. Fe3O4@HKUST-1 was thermally converted into magnetic Fe3O4@Cu/C and Fe3O4@CuO composites in different atmosphere (N2 and air). The resulting composites not only kept superparamagnetic characteristics, but also exhibited improved peroxidase-like catalytic activity and high stability when compared to the precursor Fe3O4@HKUST-1. The morphology, crystal structure, magnetic and porous properties of Fe3O4@Cu/C and Fe3O4@CuO composites were characterized, and the kinetics parameters and the influence factors on the peroxidase-mimicking activity such as temperature, pH and H2O2 concentration were evaluated. On account of the excellent peroxidase-like activity, the as-prepared Fe3O4@Cu/C and Fe3O4@CuO composites were successfully used for the catalytic removal of methylene blue (MB) dye with H2O2 oxidant. This work provides an effective way to fabricate highly reactive MOFs-derived biomimetic catalysts, which have potential applications in bioassays and pollutant degradation.

Graphic Abstract

Fe3O4@Cu/C and Fe3O4@CuO composites were achieved using Fe3O4 nanoparticle-encapsulated HKUST-1 as self-sacrificial templates and demonstrated excellent peroxidase-like activity.

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  1. 1.

    Wang Q, Wei H, Zhang Z, Wang E, Dong S (2018) Nanozyme: an emerging alternative to natural enzyme for biosensing and immunoassay. TrAC Trend Anal Chem 105:218–224

  2. 2.

    Lin Y, Ren J, Qu X (2014) Catalytically active nanomaterials: a promising candidate for artificial enzymes. Acc Chem Res 47:1097–1105

  3. 3.

    Jin S, Wu C, Ye Z, Ying Y (2019) Designed inorganic nanomaterials for intrinsic peroxidase mimics: a review. Sens Actuator B 283:18–34

  4. 4.

    Gao L, Zhuang J, Nie L, Zhang J, Zhang Y, Gu N, Wang T, Feng J, Yang D, Perrett S, Yan X (2007) Intrinsic peroxidase-like activity of ferromagnetic nanoparticles. Nat Nanotechnol 2:577–583

  5. 5.

    Wu J, Wang X, Wang Q, Lou Z, Li S, Zhu Y, Qin L, Wei H (2019) Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes (II). Chem Soc Rev 48:1004–1076

  6. 6.

    Song Y, Wei W, Qu X (2011) Colorimetric biosensing using smart materials. Adv Mater 23:4215–4236

  7. 7.

    Zhou Y, Liu B, Yang R, Liu J (2017) Filling in the gaps between nanozymes and enzymes: challenges and opportunities. Bioconjugate Chem 28:2903–2909

  8. 8.

    Wu J, Li S, Wei H (2018) Integrated nanozymes: facile preparation and biomedical applications. Chem Commun 54:6520–6530

  9. 9.

    Cui Y, Li B, He H, Zhou W, Chen B, Qian G (2016) Metal-organic frameworks as platforms for functional materials. Acc Chem Res 49:483–493

  10. 10.

    Li B, Wen HM, Cui Y, Zhou W, Qian G, Chen B (2016) Emerging multifunctional metal-organic framework materials. Adv Mater 28:8819–8860

  11. 11.

    Gu ZY, Park J, Raiff A, Wei Z, Zhou HC (2014) Metal-organic frameworks as biomimetic catalysts. ChemCatChem 6:67–75

  12. 12.

    Feng D, Gu ZY, Li JR, Jiang HL, Wei Z, Zhou HC (2012) Zirconium-metalloporphyrin PCN-222: mesoporous metal-organic frameworks with ultrahigh stability as biomimetic catalysts. Angew Chem Int Ed 51:10307–10310

  13. 13.

    Ai L, Li L, Zhang C, Fu J, Jiang J (2013) MIL-53(Fe): a metal-organic framework with intrinsic peroxidase-like catalytic activity for colorimetric biosensing. Chem Chem Eur J 19:15105–15108

  14. 14.

    Wang Y, Zhu Y, Binyam A, Liu M, Wu Y, Li F (2016) Discovering the enzyme mimetic activity of metal-organic framework (MOF) for label-free and colorimetric sensing of biomolecules. Biosens Bioelectron 86:432–438

  15. 15.

    Zhang JW, Zhang HT, Du ZY, Wang X, Yu SH, Jiang HL (2014) Water-stable metal-organic frameworks with intrinsic peroxidase-like catalytic activity as a colorimetric biosensing platform. Chem Commun 50:1092–1094

  16. 16.

    Zheng HQ, Liu CY, Zeng XY, Chen J, Lu J, Lin RG, Cao R, Lin ZJ, Su JW (2018) MOF-808: a metal-organic framework with intrinsic peroxidase-like catalytic activity at neutral pH for colorimetric biosensing. Inorg Chem 57:9096–9104

  17. 17.

    Mondal SS, Holdt HJ (2016) Breaking down chemical weapons by metal-organic frameworks. Angew Chem Int Ed 55(2016):42–44

  18. 18.

    Plonka AM, Wang Q, Gordon WO, Balboa A, Troya D, Guo W, Sharp CH, Senanayake SD, Morris JR, Hill CL, Frenkel AI (2017) In situ probes of capture and decomposition of chemical warfare agent simulants by Zr-based metal organic frameworks. J Am Chem Soc 139:599–602

  19. 19.

    Chen K, Wu CD (2019) Designed fabrication of biomimetic metal-organic frameworks for catalytic applications. Coord Chem Rev 378:445–465

  20. 20.

    Kaneti YV, Tang J, Salunkhe RR, Jiang X, Yu A, Wu KC, Yamauchi Y (2017) Nanoarchitectured design of porous materials and nanocomposites from metal-organic frameworks. Adv Mater 29:1604898

  21. 21.

    Liu Y, Tang Z (2013) Multifunctional nanoparticle@MOF core-shell nanostructures. Adv Mater 25:5819–5825

  22. 22.

    Yang H, Bradley SJ, Wu X, Chan A, Waterhouse GIN, Nann T, Zhang J, Kruger PE, Ma S, Telfer SG (2018) General synthetic strategy for libraries of supported multicomponent metal nanoparticles. ACS Nano 12:4594–4604

  23. 23.

    Yang H, Bradley SJ, Chan A, Waterhouse GIN, Nann T, Kruger PE, Telfer SG (2016) Catalytically active bimetallic nanoparticles supported on porous carbon capsules derived from metal–organic framework composites. J Am Chem Soc 138:11872–11881

  24. 24.

    Xuan S, Wang F, Xiang-Y J, Yu JC, Leung KC-F (2010) Facile synthesis of size-controllable monodispersed ferrite nanospheres. J Mater Chem 20:5086–5094

  25. 25.

    Li Z, Zeng HC (2014) Armored MOFs: enforcing soft microporous MOF nanocrystals with hard mesoporous silica. J Am Chem Soc 136:5631–5639

  26. 26.

    Li S, Huo F (2014) Hybrid crystals comprising metal–organic frameworks and functional particles: synthesis and applications. Nanoscale 4:591–599

  27. 27.

    Silvestre ME, Franzreb M, Weidler PG, Shekhah O, Wöll C (2013) Magnetic cores with porous coatings: growth of metal-organic frameworks on particles using liquid phase epitaxy. Adv Funct Mater 23:1210–1213

  28. 28.

    Fan S, Dong W, Huang X, Gao H, Wang J, Jin Z, Tang J, Wang G (2016) In situ-induced synthesis of magnetic Cu-CuFe2O4@HKUST-1 heterostructures with enhanced catalytic performance for selective aerobic benzylic C-H oxidation. ACS Catal 7:243–249

  29. 29.

    Ke F, Yuan YP, Qiu LG, Shen Y-H, Xie A-J, Zhu J-F, Tian X-Y, Zhang L-D (2011) Facile fabrication of magnetic metal-organic framework nanocomposites for potential targeted drug delivery. J Mater Chem 21:3843–3848

  30. 30.

    Howarth AJ, Liu Y, Li P, Li Z, Wang TC, Hupp JT, Farha OK (2016) Chemical, thermal and mechanical stabilities of metal-organic frameworks. Nat Rev Mater 1:1–15

  31. 31.

    Zhang YF, Qiu LG, Yuan YP, Zhu Y-J, Jiang X, Xiao J-D (2014) Magnetic Fe3O4@C/Cu and Fe3O4@CuO core-shell composites constructed from MOF-based materials and their photocatalytic properties under visible light. Appl Catal B 144:863–869

  32. 32.

    Das R, Pachfule P, Banerjee R, Poddar P (2012) Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides. Nanoscale 4:591–599

  33. 33.

    DeCoste JB, Peterson GW, Schindler BJ, Killops KL, Browe MA, Mahle JJ (2013) The effect of water adsorption on the structure of the carboxylate containing metal-organic frameworks Cu-BTC, Mg-MOF-74, and UiO-66. J Mater Chem A 1:11922–11932

  34. 34.

    Hu L, Huang Y, Zhang F, Chen Q (2013) CuO/Cu2O composite hollow polyhedrons fabricated from metal-organic framework templates for lithium-ion battery anodes with a long cycling life. Nanoscale 5:4186–4190

  35. 35.

    Dong W, Zhuang Y, Li S, Zhang X, Chai H, Huang Y (2018) High peroxidase-like activity of metallic cobalt nanoparticles encapsulated in metal-organic frameworks derived carbon for biosensing. Sens. Actuators B 255:2050–2057

  36. 36.

    Wu Y, Ma Y, Xu G, Wei F, Ma Y, Song Q, Wang X, Tang T, Song Y, Shi M, Xu X, Hu Q (2017) Metal-organic framework coated Fe3O4 magnetic nanoparticles with peroxidase-like activity for colorimetric sensing of cholesterol. Sens Actuators B 249:195–202

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This work was supported by National Natural Science Foundation of China (Grants 21878229, 21475095), The Science and Technology Plans of Tianjin (18PTSYJC00180).

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Correspondence to Yan-Feng Huang.

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Huang, Y., Zhang, L., Ma, L. et al. Fe3O4@Cu/C and Fe3O4@CuO Composites Derived from Magnetic Metal–Organic Frameworks Fe3O4@HKUST-1 with Improved Peroxidase-Like Catalytic Activity. Catal Lett 150, 815–825 (2020). https://doi.org/10.1007/s10562-019-02964-8

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  • Peroxidase mimic
  • Magnetic
  • Metal–organic frameworks
  • Methylene blue
  • Degradation