A carbon paste electrode modified with a metal-organic framework of type MIL-101(Fe) for voltammetric determination of citric acid
- 165 Downloads
A carbon paste electrode (CPE) modified with a metal-organic framework composite of type MIL-101(Fe) is described for determination of citric acid (CA). The electrochemical activity of the modified CPE was studied by cyclic voltammetry and differential pulse voltammetry. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, N2 adsorption-desorption isotherms and X-ray powder diffraction were used for characterization of the MIL-101(Fe). Under optimized electrochemical conditions, the anodic peak current, best measured at working potentials around 0.02 V (vs. Ag/AgCl); decreases linearly in the 5.0 to 100 μM CA concentration range, and the detection limit is 4.0 μM (at S/N = 3). The electrode exhibits good selectivity for CA, with no significant interference in the wide pH range of 3.0 to 9.0. The electrochemical sensitivity of the MIL-CPE is −0.67 μA·μM−1·cm−2. The method was successfully applied to the determination of CA in some commercial beverages. The good recoveries (98–102%) and the agreement of data with those obtained by HPLC indicate the applicability of the method.
KeywordsMOFs Porous materials Sensor Electrochemistry Beverage Cyclic voltammetry Differential pulse voltammetry
The authors express their gratitude to Shiraz University Research Council for the support of this work (grant no. 95GCU2M172254).
Compliance with ethical standards
The author(s) declare that they have no competing interests.
- 3.Aijaz A, Karkamkar A, Choi YJ, Tsumori N, Rönnebro E, Autrey T, Shioyama H, Xu Q (2012) Immobilizing highly catalytically active Pt nanoparticles inside the pores of metal–organic framework: a double solvents approach. J Am Chem Soc 134(34):13926–13929. https://doi.org/10.1021/ja3043905 CrossRefPubMedGoogle Scholar
- 13.Horcajada P, Chalati T, Serre C, Gillet B, Sebrie C, Baati T, Eubank JF, Heurtaux D, Clayette P, Kreuz C (2010) Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging. Nat Mater 9(2):172–178. https://doi.org/10.1038/nmat2608 CrossRefPubMedGoogle Scholar
- 16.Lin H, Wang X, Hu H, Chen B, Liu G (2009) A novel copper (II) complex constructed with mixed ligands of biphenyl-4, 4′-dicarboxylic acid (H 2 bpdc) and dipyrido [3, 2-d: 2′, 3′-f] quinoxaline (Dpq): synthesis, structure, electrochemistry and electrocatalysis. Solid State Sci 11(3):643–650. https://doi.org/10.1016/j.solidstatesciences.2008.10.007 CrossRefGoogle Scholar
- 17.Nguyen TLA, Devic T, Mialane P, Riviere E, Sonnauer A, Stock N, Demir-Cakan R, Morcrette M, Livage C, Marrot J (2010) Reinvestigation of the MII (M= Ni, co)/TetraThiafulvaleneTetraCarboxylate system using high-throughput methods: isolation of a molecular complex and its single-crystal-to-single-crystal transformation to a two-dimensional coordination polymer. Inorg Chem 49(22):10710–10717. https://doi.org/10.1021/ic101906u CrossRefGoogle Scholar
- 25.do Nascimento RF, Selva TMG, Ribeiro WF, Belian MF, Angnes L, do Nascimento VB (2013) Flow-injection electrochemical determination of citric acid using a cobalt (II)–phthalocyanine modified carbon paste electrode. Talanta 105:354–359. https://doi.org/10.1016/j.talanta.2012.10.055 CrossRefPubMedGoogle Scholar
- 28.Fernandes DM, Barbosa AD, Jo P, Balula SS, Cunha-Silva L, Freire C (2013) Novel composite material polyoxovanadate@ MIL-101 (Cr): a highly efficient electrocatalyst for ascorbic acid oxidation. ACS Appl Mater Interfaces 5(24):13382–13390. https://doi.org/10.1021/am4042564 CrossRefPubMedGoogle Scholar
- 31.Honeychurch KC, Gilbert L, Hart JP (2010) Electrocatalytic behaviour of citric acid at a cobalt phthalocyanine-modified screen-printed carbon electrode and its application in pharmaceutical and food analysis. Anal Bioanal Chem 396(8):3103–3111. https://doi.org/10.1007/s00216-010-3534-x CrossRefPubMedGoogle Scholar
- 32.Themelis DG, Tzanavaras PD (2001) Reagent-injection spectrophotometric determination of citric acid in beverages and pharmaceutical formulations based on its inhibitory effect on the iron (III) catalytic oxidation of 2, 4-diaminophenol by hydrogen peroxide. Anal Chim Acta 428(1):23–30. https://doi.org/10.1016/s0003-2670(00)01221-6 CrossRefGoogle Scholar