Size and shape effects of MnFe<sub>2</sub>O<sub>4</sub> nanoparticles as catalysts for reductive degradation of dye pollutants

doi:10.1007/s11783-021-1396-4

Front. Environ. Sci. Eng.

2021, Vol. 15

Issue (5) : 108 https://doi.org/10.1007/s11783-021-1396-4

RESEARCH ARTICLE

Size and shape effects of MnFe₂O₄ nanoparticles as catalysts for reductive degradation of dye pollutants

Guowen Hu(

), Zeqi Zhang, Xuan Zhang, Tianrong Li(

)

State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China

Download: PDF(1266 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

• Size and shape-dependent MnFe₂O₄ NPs were prepared via a facile method.

• Ligand-exchange chemistry was used to prepare the hydrophilic MnFe₂O₄ NPs.

• The catalytic properties of MnFe₂O₄ NPs toward dye degradation were fully studied.

• The catalytic activities of MnFe₂O₄ NPs followed Michaelis–Menten behavior.

• All the MnFe₂O₄ NPs exhibit selective degradation to different dyes.

The magnetic nanoparticles that are easy to recycle have tremendous potential as a suitable catalyst for environmental toxic dye pollutant degradation. Rationally engineering shapes and tailoring the size of nanocatalysts are regarded as an effective manner for enhancing performances. Herein, we successfully synthesized three kinds of MnFe₂O₄ NPs with distinctive sizes and shapes as catalysts for reductive degradation of methylene blue, rhodamine 6G, rhodamine B, and methylene orange. It was found that the catalytic activities were dependent on the size and shape of the MnFe₂O₄ NPs and highly related to the surface-to-volume ratio and atom arrangements. Besides, all these nanocatalysts exhibit selectivity to different organic dyes, which is beneficial for their practical application in dye pollutant treatment. Furthermore, the MnFe₂O₄ NPs could be readily recovered by a magnet and reused more than ten times without appreciable loss of activity. The size and shape effects of MnFe₂O₄ nanoparticles demonstrated in this work not only accelerate further understanding the nature of nanocatalysts but also contribute to the precise design of nanoparticles catalyst for pollutant degradation.

Keywords Dye degradation MnFe₂O₄ nanoparticles Size and shape-control

Corresponding Author(s): Guowen Hu,Tianrong Li

Issue Date: 18 January 2021

Cite this article:

Guowen Hu,Zeqi Zhang,Xuan Zhang, et al. Size and shape effects of MnFe₂O₄ nanoparticles as catalysts for reductive degradation of dye pollutants[J]. Front. Environ. Sci. Eng., 2021, 15(5): 108.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-021-1396-4
https://academic.hep.com.cn/fese/EN/Y2021/V15/I5/108

Fig.1 TEM images and EDX of the 4 nm spherical MnFe₂O₄ NPs (A, B), 18 nm spheroidicity MnFe₂O₄ NPs (C, D), and 27 nm near-cubic MnFe₂O₄ NPs (E, F), respectively. Insets show the SAED patterns,HR-TEM images and size statistical analysis of the MnFe₂O₄ NPs.

Fig.2 (A) XRD patterns of MnFe₂O₄ NPs. (B) Magnetic behavior of MnFe₂O₄ NPs at 300K. Insets: magnetic separation of MnFe₂O₄-DIB-PEG-NH₂ NPs.

Fig.3 (A, B, C) UV-vis absorption spectrum of MB with the treatment of 1a, 1b, and 1c. Insets: changes in color of the MB aqueous solution before and after the reaction. (D) C_t/C₀vs reaction time t of 1a, 1b, and 1c to MB. (E) Relationship between -ln(C_t/C₀) and reaction time. (F) k and k’ of 1a, 1b, and 1c toward the degradation of MB.

Fig.4 C/C₀ versus reaction time for the distinct concentration of 1c (A) and NaBH₄ (B).

Fig.5 Catalytic degradation efficiency of 1a, 1b, and 1c toward R6G, RB and MO.

Fig.6 Changes in degradation efficiency of MB by 1c within 10 cycles.

1	B Bateer, C Tian, Y Qu, S Du, Y Yang, Z Ren, K Pan, H Fu (2014). Synthesis, size and magnetic properties of controllable MnFe2O4 nanoparticles with versatile surface functionalities. Dalton Transactions (Cambridge, England), 43(26): 9885–9891 https://doi.org/10.1039/c4dt00089g
2	C Cannas, A Ardu, A Musinu, D Peddis, G Piccaluga (2008). Spherical nanoporous assemblies of iso-oriented cobalt ferrite nanoparticles: synthesis, microstructure, and magnetic properties. Chemistry of Materials, 20(20): 6364–6371 https://doi.org/10.1021/cm801839s
3	Q Chen, J Zheng, Q Yang, Z Dang, L Zhang (2019). Insights into the glyphosate adsorption behavior and mechanism by a MnFe2O4@Cellulose-activated carbon magnetic hybrid. ACS Applied Materials & Interfaces, 11(17): 15478–15488 https://doi.org/10.1021/acsami.8b22386
4	R Chen, M G Christiansen, P Anikeeva (2013). Maximizing hysteretic losses in magnetic ferrite nanoparticles via model-driven synthesis and materials optimization. ACS Nano, 7(10): 8990–9000 https://doi.org/10.1021/nn4035266
5	A Chowdhury, A A Khan, S Kumari, S Hussain (2019). Superadsorbent Ni–Co–S/SDS nanocomposites for ultrahigh removal of cationic, anionic organic dyes and toxic metal ions: kinetics, isotherm and adsorption mechanism. ACS Sustainable Chemistry & Engineering, 7(4): 4165–4176 https://doi.org/10.1021/acssuschemeng.8b05775
6	R Comes, H Liu, M Khokhlov, R Kasica, J Lu, S A Wolf (2012). Directed self-assembly of epitaxial CoFe2O4–BiFeO3 multiferroic nanocomposites. Nano Letters, 12(5): 2367–2373 https://doi.org/10.1021/nl3003396
7	C V M Gopi, R Vinodh, S Sambasivam, I M Obaidat, S Singh, H J Kim (2020). Co9S8-Ni3S2/CuMn2O4-NiMn2O4 and MnFe2O4-ZnFe2O4/graphene as binder-free cathode and anode materials for high energy density supercapacitors. Chemical Engineering Journal, 381: 122640 https://doi.org/10.1016/j.cej.2019.122640
8	P Guo, G Zhang, J Yu, H Li, X Zhao (2012). Controlled synthesis, magnetic and photocatalytic properties of hollow spheres and colloidal nanocrystal clusters of manganese ferrite. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 395: 168–174 https://doi.org/10.1016/j.colsurfa.2011.12.027
9	C He, J Cheng, X Zhang, M Douthwaite, S Pattisson, Z Hao (2019). Recent advances in the catalytic oxidation of volatile organic compounds: A review based on pollutant sorts and sources. Chemical Reviews, 119(7): 4471–4568 https://doi.org/10.1021/acs.chemrev.8b00408
10	T Kamal, S B Khan, A M Asiri (2016). Synthesis of zero-valent Cu nanoparticles in the chitosan coating layer on cellulose microfibers: Evaluation of azo dyes catalytic reduction. Cellulose (London, England), 23(3): 1911–1923 https://doi.org/10.1007/s10570-016-0919-9
11	S Kampouri, K C Stylianou (2019). Dual-functional photocatalysis for simultaneous hydrogen production and oxidation of organic substances. ACS Catalysis, 9(5): 4247–4270 https://doi.org/10.1021/acscatal.9b00332
12	J Kim, H R Cho, H Jeon, D Kim, C Song, N Lee, S H Choi, T Hyeon (2017). Continuous O2-evolving MnFe2O4 nanoparticle-anchored mesoporous silica nanoparticles for efficient photodynamic therapy in hypoxic cancer. Journal of the American Chemical Society, 139(32): 10992–10995 https://doi.org/10.1021/jacs.7b05559
13	X Kong, Z y Sun, M Chen, Q Chen, Q Chen (2013). Metal-free catalytic reduction of 4-nitrophenol to 4-aminophenol by N-doped graphene. Energy & Environmental Science, 6(11): 3260–3266 https://doi.org/10.1039/c3ee40918j
14	E Lam, S Hrapovic, E Majid, J H Chong, J H Luong (2012). Catalysis using gold nanoparticles decorated on nanocrystalline cellulose. Nanoscale, 4(3): 997–1002 https://doi.org/10.1039/c2nr11558a
15	B Li, H Cao, J Yin, Y A Wu, J H Warner (2012). Synthesis and separation of dyes via Ni@ reduced graphene oxide nanostructures. Journal of Materials Chemistry, 22(5): 1876–1883 https://doi.org/10.1039/C1JM13032C
16	S Li, H Li, J Liu, H Zhang, Y Yang, Z Yang, L Wang, B Wang (2015). Highly efficient degradation of organic dyes by palladium nanoparticles decorated on 2D magnetic reduced graphene oxide nanosheets. Dalton Transactions (Cambridge, England), 44(19): 9193–9199 https://doi.org/10.1039/C5DT01036E
17	Y Li, C X Yang, H L Qian, X Zhao, X P Yan (2019). Carboxyl-functionalized covalent organic frameworks for the adsorption and removal of triphenylmethane dyes. ACS Applied Nano Materials, 2(11): 7290–7298 https://doi.org/10.1021/acsanm.9b01781
18	B Liu, Q Li, B Zhang, Y Cui, H Chen, G Chen, D Tang (2011). Synthesis of patterned nanogold and mesoporous CoFe2O4 nanoparticle assemblies and their application in clinical immunoassays. Nanoscale, 3(5): 2220–2226 https://doi.org/10.1039/c1nr10069f
19	J Liu, H Cao, J Xiong, Z Cheng (2012). Ferromagnetic hematite@graphene nanocomposites for removal of rhodamine B dye molecules from water. CrystEngComm, 14(16): 5140–5144 https://doi.org/10.1039/c2ce25578b
20	S Manzetti, E R van der Spoel, D van der Spoel (2014). Chemical properties, environmental fate, and degradation of seven classes of pollutants. Chemical Research in Toxicology, 27(5): 713–737 https://doi.org/10.1021/tx500014w
21	M L Marin, L Santos-Juanes, A Arques, A M Amat, M A Miranda (2012). Organic photocatalysts for the oxidation of pollutants and model compounds. Chemical Reviews, 112(3): 1710–1750 https://doi.org/10.1021/cr2000543
22	K B Narayanan, H H Park (2015). Homogeneous catalytic activity of gold nanoparticles synthesized using turnip (Brassica rapa L.) leaf extract in the reductive degradation of cationic azo dye. Korean Journal of Chemical Engineering, 32(7): 1273–1277 https://doi.org/10.1007/s11814-014-0321-y
23	M Pal, R Rakshit, K Mandal (2014). Surface modification of MnFe2O4 nanoparticles to impart intrinsic multiple fluorescence and novel photocatalytic properties. ACS Applied Materials & Interfaces, 6(7): 4903–4910 https://doi.org/10.1021/am405950q
24	D Pan, F Mou, X Li, Z Deng, J Sun, L Xu, J Guan (2016). Multifunctional magnetic oleic acid-coated MnFe2O4/polystyrene Janus particles for water treatment. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 4(30): 11768–11774 https://doi.org/10.1039/C6TA04010A
25	S Peng, W Meng, J Guo, B Wang, Z Wang, N Xu, X Li, J Wang, J Xu (2019). Photocatalytically stable superhydrophobic and translucent coatings generated from PDMS-Grafted-SiO2/TiO2@ PDMS with multiple applications. Langmuir, 35(7): 2760–2771 https://doi.org/10.1021/acs.langmuir.8b04247
26	X Peng, F Gao, J Zhao, J Li, J Qu, H Fan (2018). Self-assembly of a graphene oxide/MnFe2O4 motor by coupling shear force with capillarity for removal of toxic heavy metals. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 6(42): 20861–20868 https://doi.org/10.1039/C8TA06663A
27	Y Peng, Z Wang, W Liu, H Zhang, W Zuo, H Tang, F Chen, B Wang (2015). Size-and shape-dependent peroxidase-like catalytic activity of MnFe2O4 nanoparticles and their applications in highly efficient colorimetric detection of target cancer cells. Dalton Transactions (Cambridge, England), 44(28): 12871–12877 https://doi.org/10.1039/C5DT01585E
28	T Prozorov, P Palo, L Wang, M Nilsen-Hamilton, D Jones, D Orr, S K Mallapragada, B Narasimhan, P C Canfield, R Prozorov (2007). Cobalt ferrite nanocrystals: out-performing magnetotactic bacteria. ACS Nano, 1(3): 228–233 https://doi.org/10.1021/nn700194h
29	S M Saleh (2019). ZnO nanospheres based simple hydrothermal route for photocatalytic degradation of azo dye. Spectrochimica Acta. Part A: Molecular and Biomolecular Spectroscopy, 211: 141–147 https://doi.org/10.1016/j.saa.2018.11.065
30	L Su, S Lei, L Liu, L Liu, Y Zhang, S Shi, X Yan (2018). Sprinkling MnFe2O4 quantum dots on nitrogen-doped graphene sheets: the formation mechanism and application for high-performance supercapacitor electrodes. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 6(21): 9997–10007 https://doi.org/10.1039/C8TA02982B
31	K Thakur, B Kandasubramanian (2019). Graphene and graphene oxide-based composites for removal of organic pollutants: A review. Journal of Chemical & Engineering Data, 64(3): 833–867 https://doi.org/10.1021/acs.jced.8b01057
32	C R Vestal, Z J Zhang (2003). Effects of surface coordination chemistry on the magnetic properties of MnFe2O4 spinel ferrite nanoparticles. Journal of the American Chemical Society, 125(32): 9828–9833 https://doi.org/10.1021/ja035474n
33	L Wang, G Hu, Z Wang, B Wang, Y Song, H Tang (2015a). Highly efficient and selective degradation of methylene blue from mixed aqueous solution by using monodisperse CuFe2O4 nanoparticles. RSC Advances, 5(90): 73327–73332 https://doi.org/10.1039/C5RA10543A
34	N Wang, X Ma, Y Wang, J Yang, Y Qian (2015b). Porous MnFe2O4 microrods as advanced anodes for Li-ion batteries with long cycle lifespan. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 3(18): 9550–9555 https://doi.org/10.1039/C5TA00828J
35	Q Wang, B Zhang, X Lu, X Zhang, H Zhu, B Li (2018). Multifunctional 3D K2Ti6O13 nanobelt-built architectures towards wastewater remediation: selective adsorption, photodegradation, mechanism insight and photoelectrochemical investigation. Catalysis Science & Technology, 8(23): 6180–6195 https://doi.org/10.1039/C8CY01684D
36	Z Wang, J Liu, T Li, J Liu, B Wang (2014). Controlled synthesis of MnFe2O4 nanoparticles and Gd complex-based nanocomposites as tunable and enhanced T1/T2-weighted MRI contrast agents. Journal of Materials Chemistry. B, Materials for Biology and Medicine, 2(29): 4748–4753 https://doi.org/10.1039/c4tb00342j
37	H Wu, G Liu, X Wang, J Zhang, Y Chen, J Shi, H Yang, H Hu, S Yang (2011). Solvothermal synthesis of cobalt ferrite nanoparticles loaded on multiwalled carbon nanotubes for magnetic resonance imaging and drug delivery. Acta Biomaterialia, 7(9): 3496–3504 https://doi.org/10.1016/j.actbio.2011.05.031
38	Z F Xu, C F Sun, W Y Duan, E J Zhang, W Dai, X J Zheng, F Y Liu, X X Tan (2013). Clinical anatomical study and evaluation of the use of the free anteromedial thigh perforator flaps in reconstructions of the head and neck. British Journal of Oral & Maxillofacial Surgery, 51(8): 725–730 https://doi.org/10.1016/j.bjoms.2011.11.017
39	G Zeng, N Shi, M Hess, X Chen, W Cheng, T Fan, M Niederberger (2015). A general method of fabricating flexible spinel-type oxide/reduced graphene oxide nanocomposite aerogels as advanced anodes for lithium-ion batteries. ACS Nano, 9(4): 4227–4235 https://doi.org/10.1021/acsnano.5b00576
40	Q Zhang, R Dong, Y Wu, W Gao, Z He, B Ren (2017). Light-driven Au-WO3@C Janus micromotors for rapid photodegradation of dye pollutants. ACS Applied Materials & Interfaces, 9(5): 4674–4683 https://doi.org/10.1021/acsami.6b12081
41	X J Zhang, G S Wang, W Q Cao, Y Z Wei, J F Liang, L Guo, M S Cao (2014). Enhanced microwave absorption property of reduced graphene oxide (RGO)-MnFe2O4 nanocomposites and polyvinylidene fluoride. ACS Applied Materials & Interfaces, 6(10): 7471–7478 https://doi.org/10.1021/am500862g

[1]

FSE-20171-OF-HGW_suppl_1

Download

Viewed

Full text

Abstract

Cited

Shared

Discussed