Fabrication of a novel electrochemical sensor based on MnFe₂O₄/graphene modified glassy carbon electrode for the sensitive detection of bisphenol A

Abstract

Manganese ferrite (MnFe₂O₄) has the advantages of simple preparation, high resistivity, and high crystal symmetry. Herein, we have developed an electrochemical sensor utilizing graphene and MnFe₂O₄ nanocomposites modified glassy carbon electrode (GCE), which is very efficient and sensitive to detect bisphenol A (BPA). MnFe₂O₄/graphene (GR) was synthesized by immobilizing the MnFe₂O₄ microspheres on the graphene nanosheets via a simple one-pot solvothermal method. The morphology and structure of the MnFe₂O₄/GR nanocomposite have been characterized through scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). In addition, electrochemical properties of the modified materials are comparably explored by means of cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV). Under the optimal conditions, the proposed electrochemical sensor for the detection of BPA has a linear range of 0.8–400 µmol/L and a detection limit of 0.0235 µmol/L (S/N=3) with high sensitivity, good selectivity and high stability. In addition, the proposed sensor was used to measure the content of BPA in real water samples with a recovery rate of 97.94%–104.56%. At present, the synthesis of MnFe₂O₄/GR provides more opportunities for the electrochemical detection of BPA in practical applications.

Keywords

MnFe₂O₄ / graphene / electrochemical sensor / bisphenol A

References

[[1]] Nandy S, Latwal M, Pandey G, et al.. Synthesis of nanostructured ferrites and cation distribution studies by X-ray magnetic circular dichroism, Mössbauer spectroscopy, and X-ray absorption spectroscopy [J]. Journal of Electronic Materials, 2022, 51(12): 6663-6688,

[[2]] Flores-Lasluisa J X, Salinas-Torres D, López-Ramon M V, et al.. Electrocatalytic activity of calcined manganese ferrite solid nanospheres in the oxygen reduction reaction [J]. Environmental Research, 2022, 204: 112126,

[[3]] Fu M, Zhu Z-t, Zhuang Q-r, et al.. In situ growth of manganese ferrite nanorods on graphene for supercapacitors [J]. Ceramics International, 2020, 46(18): 28200-28205,

[[4]] Chen Z, Harris V G. Ferrite film growth on semiconductor substrates towards microwave and millimeter wave integrated circuits [J]. Journal of Applied Physics, 2012, 112(8): 081101,

[[5]] Nigam A, Pawar S J. Structural, magnetic, and antimicrobial properties of zinc doped magnesium ferrite for drug delivery applications [J]. Ceramics International, 2020, 46(4): 4058-4064,

[[6]] Pattanaik M S, Varma V B, Cheekati S K, et al.. Optimal ferrofluids for magnetic cooling devices [J]. Scientific Reports, 2021, 11(1): 24167,

[[7]] Lu L-l, Hu X-h, Zeng R-j, et al.. Dual-mode colorimetric-photothermal sensing platform of acetylcholinesterase activity based on the peroxidase-like activity of Fe-N-C nanozyme [J]. Analytica Chimica Acta, 2022, 1229: 340383,

[[8]] Yu Z-c, Xu J-h, Li Y-x, et al.. Ferroelectric perovskite-enhanced photoelectrochemical immunoassay with the photoexcited charge-transfer of a built-in electric field [J]. Journal of Materials Chemistry C, 2021, 9(40): 14351-14358,

[[9]] Wan X-y, Zeng R-j, Wang X, et al.. High-entropy effect with hollow (ZnCdFeMnCu)_xS nanocubes for photoelectrochemical immunoassay [J]. Biosensors and Bioelectronics, 2023, 237: 115535,

[[10]] Huang X, Lin Q-y, Gong H-x, et al.. Bio-inspired nanozyme with ultra-thin Fe-Bi₂O₂S nanosheets for in situ amplified photoelectrochemical immunoassay of cancer-related protein [J]. Analytica Chimica Acta, 2023, 1252: 341058,

[[11]] Mondal D K, Borgohain C, Paul N, et al.. Tuning hyperthermia efficiency of MnFe₂O₄/ZnS nanocomposites by controlled ZnS concentration [J]. Journal of Materials Research and Technology, 2019, 8(6): 5659-5670,

[[12]] Akhlaghi N, Najafpour-Darzi G. Manganese ferrite (MnFe₂O₄) nanoparticles: From synthesis to application-a review [J]. Journal of Industrial and Engineering Chemistry, 2021, 103: 292-304,

[[13]] Asghar K, Qasim M, Das D. Preparation and characterization of mesoporous magnetic MnFe₂O₄@mSiO₂ nanocomposite for drug delivery application [J]. Materials Today: Proceedings, 2020, 26: 87-93

[[14]] Bao Y-z, Xing X, Huang H, et al.. Effect of alkaline environment on the electrochemical performance of manganese ferrate materials in lithium-ion battery cathode materials [J]. Inorganic Chemistry Communications, 2022, 146: 110114,

[[15]] Gong H-x, Hu X-h, Zeng R-j, et al.. CRISPR/Cas12a-based photoelectrochemical sensing of microRNA on reduced graphene oxide-anchored Bi₂WO₆ coupling with catalytic hairpin assembly [J]. Sensors and Actuators B: Chemical, 2022, 369: 132307,

[[16]] Zeng R-j, Luo Z-b, Zhang L-j, et al.. Platinum nanozyme-catalyzed gas generation for pressure-based bioassay using polyaniline nanowires-functionalized graphene oxide framework [J]. Analytical Chemistry, 2018, 90(20): 12299-12306,

[[17]] Nauman Javed R M, Al-Othman A, Tawalbeh M, et al.. Recent developments in graphene and graphene oxide materials for polymer electrolyte membrane fuel cells applications [J]. Renewable and Sustainable Energy Reviews, 2022, 168: 112836,

[[18]] Tareen A K, Khan K, Iqbal M, et al.. Recent advances in novel graphene: New horizons in renewable energy storage technologies [J]. Journal of Materials Chemistry C, 2022, 10(32): 11472-11531,

[[19]] Zandi-Atashbar N, Ensafi A A, Ahoor A H. Magnetic Fe₂CuO₄/rGO nanocomposite as an efficient recyclable catalyst to convert discard tire into diesel fuel and as an effective mercury adsorbent from wastewater [J]. Journal of Cleaner Production, 2018, 172: 68-80,

[[20]] Zhang Y-y, Wan Q-j, Yang N-jun. Recent advances of porous graphene: Synthesis, functionalization, and electrochemical applications [J]. Small, 2019, 15(48): e1903780,

[[21]] Moghaddam H M, Beitollahi H, Tajik S, et al.. Fabrication of novel TiO₂ nanoparticles/Mn(III) salen doped carbon paste electrode: Application as electrochemical sensor for the determination of hydrazine in the presence of phenol [J]. Environmental Monitoring and Assessment, 2015, 187(7): 407,

[[22]] Tajik S, Orooji Y, Karimi F, et al.. High performance of screen-printed graphite electrode modified with Ni-Mo-MOF for voltammetric determination of amaranth [J]. Journal of Food Measurement and Characterization, 2021, 15(5): 4617-4622,

[[23]] Moghaddam H M, Beitollahi H, Tajik S, et al.. Voltammetric determination of droxidopa in the presence of carbidopa using a nanostructured base electrochemical sensor [J]. Russian Journal of Electrochemistry, 2017, 53(5): 452-460,

[[24]] Baghbamidi S E, Beitollahi H, Mohammadi S Z, et al.. Nanostructure-based electrochemical sensor for the voltammetric determination of benserazide, uric acid, and folic acid [J]. Chinese Journal of Catalysis, 2013, 34(10): 1869-1875,

[[25]] Beitollahi H, Tajik S, Maleh H K, et al.. Application of a 1-benzyl-4-ferrocenyl-1H-[1, 2, 3]-triazole/carbon nanotube modified glassy carbon electrode for voltammetric determination of hydrazine in water samples [J]. Applied Organometallic Chemistry, 2013, 27(8): 444-450,

[[26]] Tajik S, Beitollahi H, Mohammadi S Z, et al.. Recent developments in electrochemical sensors for detecting hydrazine with different modified electrodes [J]. RSC Advances, 2020, 10(51): 30481-30498,

[[27]] Tarafdar A, Sirohi R, Balakumaran P A, et al.. The hazardous threat of Bisphenol A: Toxicity, detection and remediation [J]. Journal of Hazardous Materials, 2022, 423: 127097,

[[28]] Luo H-y, Lin X-g, Peng Z-j, et al.. Rapid and sensitive detection of bisphenol A based on self-assembly [J]. Micromachines, 2019, 11(1): 41,

[[29]] Karrat A, Amine A. Solid-phase extraction combined with a spectrophotometric method for determination of Bisphenol-a in water samples using magnetic molecularly imprinted polymer [J]. Microchemical Journal, 2021, 168: 106496,

[[30]] Wang L, Cao H-x, Pan C-g, et al.. A fluorometric aptasensor for bisphenol a based on the inner filter effect of gold nanoparticles on the fluorescence of nitrogen-doped carbon dots [J]. Mikrochimica Acta, 2018, 186(1): 28,

[[31]] Yin W-m, Wu L, Ding F, et al.. Surface-imprinted SiO₂@Ag nanoparticles for the selective detection of BPA using surface enhanced Raman scattering [J]. Sensors and Actuators B: Chemical, 2018, 258: 566-573,

[[32]] Liu Y-c, Wang D, Du F-y, et al.. Dummy-template molecularly imprinted micro-solid-phase extraction coupled with high-performance liquid chromatography for bisphenol A determination in environmental water samples [J]. Microchemical Journal, 2019, 145: 337-344,

[[33]] Bodur S, Erarpat S, Bozyigit G D, et al.. A sensitive determination method for trace bisphenol A in bottled water and wastewater samples: Binary solvent liquid phase microextraction-quadrupole isotope dilution-gas chromatography-mass spectrometry [J]. Microchemical Journal, 2020, 159: 105532,

[[34]] Zhang Y-y, Zhang W-w, Zhang L-m, et al.. A molecularly imprinted electrochemical BPA sensor based on multi-walled carbon nanotubes modified by CdTe quantum dots for the detection of bisphenol A [J]. Microchemical Journal, 2021, 170: 106737,

[[35]] Ali M Y, Alam A U, Howlader M M R. Fabrication of highly sensitive bisphenol A electrochemical sensor amplified with chemically modified multiwall carbon nanotubes and β-cyclodextrin [J]. Sensors and Actuators B: Chemical, 2020, 320: 128319,

[[36]] Ekomo V M, Branger C, Bikanga R, et al.. Detection of bisphenol A in aqueous medium by screen printed carbon electrodes incorporating electrochemical molecularly imprinted polymers [J]. Biosensors and Bioelectronics, 2018, 112: 156-161,

[[37]] Beitollahi H, Garkani-Nejad F, Tajik S, et al.. Voltammetric determination of acetaminophen and tryptophan using a graphite screen printed electrode modified with functionalized graphene oxide nanosheets within a Fe₃O₄@SiO₂ nanocomposite [J]. Iranian Journal of Pharmaceutical Research, 2019, 18(1): 80-90

[[38]] Beitollahi H, Shahsavari M, Sheikhshoaie I, et al.. Amplified electrochemical sensor employing screen-printed electrode modified with Ni-ZIF-67 nanocomposite for high sensitive analysis of Sudan I in present bisphenol A [J]. Food and Chemical Toxicology, 2022, 161: 112824,

[[39]] Cai W-h, Lai T, Dai W-l, et al.. A facile approach to fabricate flexible all-solid-state supercapacitors based on MnFe₂O₄/graphene hybrids [J]. Journal of Power Sources, 2014, 255: 170-178,

[[40]] Folorunso O, Hamam Y, Sadiku R, et al.. Electrical resistance control model for polypyrrole-graphene nanocomposite: Energy storage applications [J]. Materials Today Communications, 2021, 26: 101699,

[[41]] Okla M K, Harini G, Dawoud T M, et al.. Fabrication of MnFe₂O₄ spheres modified CeO₂ nano-flakes for sustainable photodegradation of MB dye and antimicrobial activity: A brief computational investigation on reactive sites and degradation pathway [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 641: 128566,

[[42]] Varghese S P, Babu B, Prasannachandran R, et al.. Enhanced electrochemical properties of Mn₃O₄/graphene nanocomposite as efficient anode material for lithium ion batteries [J]. Journal of Alloys and Compounds, 2019, 780: 588-596,

[[43]] Ajatta M A, Akinola S A, Osundahunsi O F, et al.. Effect of roasting on the chemical composition, functional characterisation and antioxidant activities of three varieties of marble vine (Dioclea reflexa): An underutilised plant [J]. Heliyon, 2021, 7(5): e07107,

[[44]] Hu H-j, Wageh S, Al-Ghamdi A A, et al.. NiFe-LDH nanosheet/carbon fiber nanocomposite with enhanced anionic dye adsorption performance [J]. Applied Surface Science, 2020, 511: 145570,

[[45]] JOSE ANTONY T, THIRUNAVUKKARASU K, JAGANNATHAN K. Structural, morphological and magnetic analysis of hydrothermally synthesized MnFe₂O₄ magnetic nanoferrites [J]. Materials Today: Proceedings, 2023. DOI: https://doi.org/10.1016/j.matpr.2023.03.051.

[[46]] Zhang H-m, Tong X, Xiao H-q, et al.. Promoting the performance of electrooxidation-PMS system for degradation of tetracycline by introduction of MnFe₂O₄/CNT as a third-electrode [J]. Separation and Purification Technology, 2022, 294: 121171,

[[47]] Wang H, Shang J, Xiao Z-l, et al.. Novel construction of carbon bonds in CeO₂@C with efficiently photocatalytic activity [J]. Dyes and Pigments, 2020, 182: 108669,

[[48]] Zhou S-l, Chen X-h, Yu P, et al.. Nitrogen-doped carbon nanotubes as an excellent substrate for electroless deposition of Pd nanoparticles with a high efficiency toward the hydrogen evolution reaction [J]. Electrochemistry Communications, 2018, 90: 91-95,

[[49]] He J-s, Zheng H, Ni F, et al.. Design and optimization of a novel Y-Fe-GO magnetic adsorbent for simultaneous removal of tetracycline and arsenic and adsorption mechanisms [J]. Chemical Engineering Journal, 2023, 457: 141195,

[[50]] Jia Y, Huang X-p, Huang K-h, et al.. Synthesis, flotation performance and adsorption mechanism of 3- (ethylamino) -N-phenyl-3-thioxopropanamide onto galena/sphalerite surfaces[J]. Journal of Industrial and Engineering Chemistry, 2019, 77: 416-425,

[[51]] Han H-l, Yin W-z, Yang B, et al.. Adsorption behavior of sodium oleate on iron minerals and its effect on flotation kinetics [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 647: 129108,

[[52]] Fan L-q, Wang X-d, Miao J-x, et al.. Core-shell structured Fe0/Mn0@Fe/Mn oxides bimetallic nanocomposites as novel heterogeneous electro-Fenton catalysts for methylene blue removal [J]. Journal of Molecular Liquids, 2023, 383: 122069,

[[53]] Li W, Zhao Z-y, Yang W, et al.. Immobilization of bovine hemoglobin on Au nanoparticles/MoS₂ nanosheets-Chitosan modified screen-printed electrode as chlorpyrifos biosensor [J]. Enzyme and Microbial Technology, 2022, 154: 109959,

[[54]] Dong P-f, Li N, Zhao H-y, et al.. POMs as active center for sensitively electrochemical detection of bisphenol A and acetaminophen [J]. Chemical Research in Chinese Universities, 2019, 35(4): 592-597,

[[55]] Cai J-y, Sun B-l, Li W-y, et al.. Novel nanomaterial of porous graphene functionalized black phosphorus as electrochemical sensor platform for bisphenol A detection [J]. Journal of Electroanalytical Chemistry, 2019, 835: 1-9,

[[56]] Wang M-x, Shi Y-f, Zhang Y-b, et al.. Sensitive electrochemical detection of bisphenol A using molybdenum disulfide/Au nanorod composites modified glassy carbon electrode [J]. Electroanalysis, 2017, 29: 2620-2627,

[[57]] Shen R-y, Zhang W-m, Yuan Y, et al.. Electrochemical detection of bisphenol A at graphene/melamine nanoparticle-modified glassy carbon electrode [J]. Journal of Applied Electrochemistry, 2015, 45(4): 343-352,

[[58]] Shen M, Li W, Chen F-z, et al.. A ratiometric electrochemical sensor for bisphenol A detection based on Ag@Fe₃O₄-rGO composite [J]. Microchemical Journal, 2023, 186: 108315,

[[59]] Amorim I, Yu Z-p, Liu L-f, et al.. Cobalt-nickel phosphide supported on reduced graphene oxide for sensitive electrochemical detection of bisphenol A [J]. Heliyon, 2024, 10(2): e24070,

[[60]] Jodar L V, Orzari L O, Ortolani T S, et al.. Electrochemical sensor based on casein and carbon black for bisphenol A detection [J]. Electroanalysis, 2019, 31(11): 2162-2170,

[[61]] Lou C-q, Jing T, Tian J-z, et al.. 3-Dimensional graphene/Cu/Fe₃O₄ composites: Immobilized laccase electrodes for detecting bisphenol A [J]. Journal of Materials Research, 2019, 34(17): 2964-2975,

[[62]] Jaballah M B, Messaoud N B, Dridi C. Development of cost-effective and sustainable sensing nanoplatform based on green AgNPs for the determination of BPA in water [J]. Journal of Materials Science: Materials in Electronics, 2022, 33(9): 6981-6998

[[63]] Rajendran J, Kannan T S, Dhanasekaran L S, et al.. Preparation of 2D Graphene/MXene nanocomposite for the electrochemical determination of hazardous bisphenol A in plastic products [J]. Chemosphere, 2022, 287: 132106,

[[64]] Kanagavalli P, Senthil K S. Stable and sensitive amperometric determination of endocrine disruptor bisphenol A at residual metal impurities within SWCNT [J]. Electroanalysis, 2018, 30(3): 445-452,

[[65]] Rasheed P A, Pandey R P, Jabbar K A, et al.. Platinum nanoparticles/TLQT (MXene) composite for the effectual electrochemical sensing of Bisphenol A in aqueous media [J]. Journal of Electroanalytical Chemistry, 2021, 880: 114934,

[[66]] Han E, Pan Y-y, Li L, et al.. Development of sensitive electrochemical sensor based on chitosan/MWCNTs-AuPtPd nanocomposites for detection of bisphenol A [J]. Chemosensors, 2023, 11(6): 331,

[[67]] Zhao Y, Zhang S, Yao W, et al.. Design and synthesis of hierarchical MnO - Fe₃O₄@C/expanded graphite composite for sensitive electrochemical detection of bisphenol A [J]. Talanta, 2024, 269: 125453,