Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2024 Oct 11;10(20):e39241.
doi: 10.1016/j.heliyon.2024.e39241. eCollection 2024 Oct 30.

CoFe-MOF nanoarray as flexible microelectrode for electrochemical detection of catechol in water samples

S Arivuselvan  1   2 , Mari Elancheziyan  3 , Raji Atchudan  4   5 , Deivasigamani Ranjith Kumar  6 , E Sivasurya  1   2 , S Philomina Mary  7 , Pandi Muthirulan  8 , Keehoon Won  3 , Manoj Devaraj  1   2
Affiliations

CoFe-MOF nanoarray as flexible microelectrode for electrochemical detection of catechol in water samples

S Arivuselvan et al. Heliyon. .

Abstract

A simple, selective, and straightforward enzyme-free electrochemical sensor has been designed and developed using cobalt hexacyanoferrate metal-organic framework (CoFe-MOF) nanoarray. The prepared CoFe-MOF nanoarray has been successfully grown over a carbon cloth (CC) to form CoFe-MOF/CC as a flexible microelectrode for the detection of catechol. The surface of the activated CC was covered uniformly with CoFe-MOF in the form of nanoarray and exhibited double-shelled cubic morphology. The CoFe-MOF/CC nanoarray microelectrode showed a pair of well-defined redox peaks corresponding to the [Fe(CN)6]4-/3- redox signal. Interestingly, the fabricated nanoarray microelectrode has displayed superior peak current at lower onset potential with high electrochemical response compared to unmodified potassium hexacyanoferrate (K3 [Fe(CN)6]) over CC microelectrode and bare activated CC. Further, the developed CoFe-MOF/CC nanoarray microelectrode for the oxidation of catechol was examined with consecutive injections of catechol. A fast and noticeable improvement in oxidation peak current was observed, thus representing the excellent electrocatalytic oxidation of catechol at the modified nanoarray microelectrode. Besides, CoFe-MOF/CC microelectrode exhibits an excellent linear response over a concentration range from 0.005 to 2.8 mM with low detection limit (LOD) and high sensitivity of 0.002 mM (S/N = 3) and 205.99 μA/mM, respectively. Moreover, the prepared nonenzymatic sensor showed outstanding stability, acceptable reproducibility, and repeatability, along with good interference ability. Catechol in spiked water samples was successfully quantified.

Keywords: Catechol; Cyclic voltammetry; Electrochemical sensor; Nanoarray microelectrode; Nonenzymatic sensor; Redox mediator; Water samples.

PubMed Disclaimer

Conflict of interest statement

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Figures

Image 1
Graphical abstract
Fig. 1
Fig. 1
Synthesis of CoFe-MOF/CC double-shelled nanoarray microelectrode.
Fig. 2
Fig. 2
FESEM image of (a) pure activated CC, (b & c) CoFe-MOF/CC nanoarray microelectrode under different magnifications. Elemental mapping of (d) Cobalt, (f) Iron, (f) Carbon, and (g) Nitrogen.
Fig. 3
Fig. 3
(a) XRD pattern of activated CC and CoFe-MOF/CC nanoarray microelectrode. (b) XPS survey spectrum of CoFe-MOF/CC nanoarray microelectrode. Core level scan of (c) Co 2p, (d) Fe 2p, (e) C 1s, and (f) N 1s.
Fig. 4
Fig. 4
(a) EIS curves of bare activated CC and CoFe-MOF/CC were measured in 0.1 M KCl containing 2.5 mM [Fe(CN)6]3-/4-. (b) Histogram bar diagram shows Rct for the activated CC and CoFe-MOF/CC. (c) CVs cures of activated CC, K3 [Fe(CN)6]/CC, and CoFe-MOF/CC were recorded in 0.1 M KCl. (d) Histogram bar shows Ipa and Ipc responses for activated CC, K3 [Fe(CN)6]/CC, and CoFe-MOF/CC.
Fig. 5
Fig. 5
(a) Cyclic voltammograms of CoFe-MOF/CC nanoarray microelectrode at various scan rates from 10 to 100 mV/s in 0.1 M KCl containing 15 μM catechol. (b) Corresponding linear plot of oxidation and reduction peak currents against scan rates.
Fig. 6
Fig. 6
(a) CVs of bare activated CC, K3 [Fe(CN)6]/CC, and CoFe-MOF/CC nanoarray microelectrode in 0.1 KCl containing 20 μM catechol. (b) CVs of CoFe-MOF/CC nanoarray microelectrode with increasing concentration of catechol. (c) Amperometric i-t response of CoFe-MOF/CC nanoarray microelectrode with increasing concentration of catechol at +0.45 V. (d) Corresponding linear curve (current vs concentration of catechol).
Fig. 7
Fig. 7
(a) Influence of electroactive interferent species (10-time excess concentration of resorcinol, hydroquinone, sert, B-Ph, glucose, ascorbic acid, uric acid, sodium chloride) on the response of 20 μM catechol. (b) Corresponding columnar diagram of the tested electroactive interferent species compared with catechol. (c) CVs of CoFe-MOF/CC nanoarray microelectrode in 0.1 M KCl for 1st cycle (red curve) and 50th cycle (blue curve) at a scan rate of 50 mV/s. (d) Demonstration of reproducibility and repeatability of the fabricated sensor.
See this image and copyright information in PMC

References

    1. Zhang M., Ye J., Fang P., Zhang Z., Wang C., Wu G. Facile electrochemical preparation of NaOH nanorods on glassy carbon electrode for ultrasensitive and simultaneous sensing of hydroquinone, catechol and resorcinol. Electrochim. Acta. 2019;317:618–627. doi: 10.1016/j.electacta.2019.06.006. - DOI
    1. Dong S., Chi L., Yang Y., He P., Wang Q., Fang Y. Simultaneous determination of dihydroxybenzene and phenylenediamine positional isomers using capillary zone electrophoresis coupled with amperometric detection. J. Separ. Sci. 2009;32:3232–3238. doi: 10.1002/jssc.200900120. - DOI - PubMed
    1. Li N., Huang J.R., Zhang H.Y., Cui M., Sun B., Zhang C., Zhao H.Y. Decoration of covalent polyoxometalate-organic frameworks with Pt nanoparticles and multiwalled carbon nanotubes for simultaneous electrochemical detection of hydroquinone and catechol. ACS Appl. Nano Mater. 2024;7:1960–1969. doi: 10.1021/acsanm.3c05232. - DOI
    1. Kaneva M., Levshakova A., Tumkin I., Fatkullin M., Gurevich E., Manshina A., Rodriguez R.D., Khairullina E. Simultaneous electrochemical detection of hydroquinone and catechol using flexible laser-induced metal-polymer composite electrodes. Microchem. J. 2024;30 doi: 10.1016/j.microc.2024.111106. - DOI
    1. Hareesha N., Manjunatha J.G., Tighezza A.M., Albaqami M.D., Sillanpaa M. Electrochemical detection and quantification of catechol based on a simple and sensitive poly (riboflavin) modified carbon nanotube paste electrode. Heliyon. 2023;9 doi: 10.1016/j.heliyon.2023.e14378. - DOI - PMC - PubMed

LinkOut - more resources