Skip to main content
Log in

Electrocatalytic oxidation of salicylic acid at a carbon paste electrode impregnated with cerium-doped zirconium oxide nanoparticles as a new sensing approach for salicylic acid determination

  • Original Paper
  • Published:
Journal of Solid State Electrochemistry Aims and scope Submit manuscript

Abstract

Cerium-doped zirconium oxide (Ce/ZrO2) was introduced as a highly efficient electrocatalyst for electrooxidation of salicylic acid (SA). The electrocatalyst material was synthesized via co-precipitation of cerium and zirconium ions, and then the resulting solid was heat-treated at high temperature to create crystallized cerium-doped zirconium oxide nanoparticles. The obtained material was characterized by scanning electron microscopy and X-ray diffraction methods. The Ce/ZrO2-modified carbon paste electrode (Ce/ZrO2-CPE) exhibited a distinct oxidative peak for SA, whereas no signal was observed for SA at unmodified carbon paste electrode at the same experimental conditions. Cyclic voltammetry and electrochemical impedance spectroscopy were applied to investigate the electrocatalytic performance of the electrode and SA electrooxidation mechanism. Square wave voltammetry was used to capture the analytical signal of SA. The electrode composition was optimized to increase the SA signal. Using the optimized electrode, it became possible to determine SA in the concentration range of 5.0–1000.0 μM with detection limit of 1.1 μM (3Sb/m). The electrode showed very high sensitivity of 1013.5 μA mM−1 cm−2 which is remarkably better than the previously reported SA sensors. The proposed method was successfully applied for the determination of SA in human serum, milk, and pharmaceutical samples.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Raskin I (1992) Role of salicylic acid in plants. Annu Rev Plant Physiol Plant Mol Biol 43(1):439–463. https://doi.org/10.1146/annurev.pp.43.060192.002255

    Article  CAS  Google Scholar 

  2. Wang LJ, Fan L, Loescher W, Duan W, Liu G, Cheng JS, Luo HB, Li SH (2010) Salicylic acid alleviates decreases in photosynthesis under heat stress and accelerates recovery in grapevine leaves. BMC Plant Biol 10(1):34–39. https://doi.org/10.1186/1471-2229-10-34

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. Ehrendorfer M, Sontag G, Pittner F (1996) Determination of salicylate in beverages and cosmetics by use of an amperometric biosensor. Fresenius J Anal Chem 356(1):75–79. https://doi.org/10.1007/s0021663560075

    Article  CAS  Google Scholar 

  4. Zhu Y, Guan X, Ji H (2009) Electrochemical solid phase micro-extraction and determination of salicylic acid from blood samples by cyclic voltammetry and differential pulse voltammetry. J Solid State Electrochem 13(9):1417–1423. https://doi.org/10.1007/s10008-008-0707-z

    Article  CAS  Google Scholar 

  5. Chem BE, Johns D, Bochner F, Imhoff OM, Rowland M (1997) Simultaneous liquid-chromatographic quantitation of salicylic acid, salicyluric acid, and gentisic acid in plasma. Clin Chem 25:1420–1425

    Google Scholar 

  6. Rainsford KD, Aspirin and the salicylates: Butterworths, London U.K., 1984, pp.245–248

  7. Saha U, Baksi K (1989) Spectrophotometric determination of salicylic acid in pharmaceutical formulations using copper(II) acetate as a colour developer. Analyst 110:739–741

    Article  Google Scholar 

  8. Sena MM, Fernandes JCB, Rover L, Poppi RJ, Kubota LT (2000) Application of two- and three-way chemometrics methods in the study of acetylsalicylic acid and ascorbic acid mixtures using ultraviolet spectrophotometry. Anal Chim Acta 409(1-2):159–170. https://doi.org/10.1016/S0003-2670(00)00707-8

    Article  CAS  Google Scholar 

  9. Villari A, Micah N, Frest M, Puglisi G (1994) Spectrofluorimetry at zero angle: determination of salicylic acid in an acetylsalicylic acid pharmaceutical formulation. Analvst 119(7):1561–1565. https://doi.org/10.1039/an9941901561

    Article  CAS  Google Scholar 

  10. Pena AM, Salinas F, Meras ID (1988) Simultaneous determination of salicyclic and salicyluric acids in urine by first-derivative synchronous fluorescence spectroscopy. Anal Chem 60(22):2493–2496. https://doi.org/10.1021/ac00173a012

    Article  Google Scholar 

  11. Buskin JN, Upton RA, Williams RL (1982) Improved liquid-chromatography of aspirin, salicylate, and salicyluric acid in plasma, with a modification for determining aspirin metabolites in urine. Clin Chem 28:1200–1203

    CAS  PubMed  Google Scholar 

  12. Sun LJ, Pan ZQ, Xie J, Liu XJ, Sun FT, Song FM, Bao N, Gu HY (2013) Electrocatalytic activity of salicylic acid on Au@Fe3O4 nanocomposites modified electrode and its detection in tomato leaves infected with Botrytis cinerea. J Electroanal Chem 706:127–132. https://doi.org/10.1016/j.jelechem.2013.07.038

    Article  CAS  Google Scholar 

  13. Wang Z, Wei F, Liu SY, Xu Q, Huang JY, Dong XY, Yu JH, Yang Q, Zhao YD, Chen H (2010) Electrocatalytic oxidation of phytohormone salicylic acid at copper nanoparticles-modified gold electrode and its detection in oilseed rape infected with fungal pathogen Sclerotinia sclerotiorum. Talanta 80(3):1277–1281. https://doi.org/10.1016/j.talanta.2009.09.023

    Article  CAS  PubMed  Google Scholar 

  14. Wang Z, Ai F, Xu Q, Yang Q, Yu JH, Huang WH, Zhao YD (2010) Electrocatalytic activity of salicylic acid on the platinum nanoparticles modified electrode by electrochemical deposition. Colloid Surface B 76(1):370–374. https://doi.org/10.1016/j.colsurfb.2009.10.038

    Article  CAS  Google Scholar 

  15. Chrzescijanska E, Wudarska E, Kusmierek E, Rynkowski J (2014) Study of acetylsalicylic acid electroreduction behavior at platinum electrode. J Electroanal Chem 713:17–21. https://doi.org/10.1016/j.jelechem.2013.11.015

    Article  CAS  Google Scholar 

  16. Park J, Eun C (2016) Electrochemical behavior and determination of salicylic acid at carbon-fiber electrodes. Electrochim Acta 194:346–356. https://doi.org/10.1016/j.electacta.2016.02.103

    Article  CAS  Google Scholar 

  17. Papouchado L, Petrie G, Adams RN (1972) Anodic-oxidation pathways of phenolic compounds: Part 1. Anodic hydroxylation reactions. J Electroanal Chem 38(2):389–395. https://doi.org/10.1016/S0022-0728(72)80349-8

    Article  CAS  Google Scholar 

  18. Koile RC, Johnson DC (1979) Electrochemical removal of phenolic films from a platinum anode. Anal Chem 51(6):741–744. https://doi.org/10.1021/ac50042a037

    Article  CAS  Google Scholar 

  19. Lupu S, Ion I, Ion AC (2009) Voltammetric determination of phenol at platinum electrodes modified with polypyrrole doped with ferricyanide. Rev Roum Chim 54:351–357

    CAS  Google Scholar 

  20. Alizadeh T, Amjadi S (2017) Indirect voltammetric determination of nicotinic acid by using a graphite paste electrode modified with reduced graphene oxide and a molecularly imprinted polymer. Microchim Acta 184:2687–2695

    Article  CAS  Google Scholar 

  21. Alizadeh T, Ganjali MR, Rafie F (2017) Trace level and highly selective determination of urea in various real samples based upon voltammetric analysis of diacetyl monoxime-urea reaction product on the carbon nanotube/carbon paste electrode. Anal Chim Acta 974:54–62. https://doi.org/10.1016/j.aca.2017.04.039

    Article  CAS  PubMed  Google Scholar 

  22. Raoof JB, Ojani R, Kolbadinezhad M (2009) Voltammetric sensor for glutathione determination based on ferrocene-modified carbon paste electrode. J Solid State Electrochem 13(9):1411–1416. https://doi.org/10.1007/s10008-008-0690-4

    Article  CAS  Google Scholar 

  23. Alizadeh T, Ganjali MR, Rafiei F, Akhoundian M (2017) Synthesis of nano-sized timolol-imprinted polymer via ultrasonication assisted suspension polymerization in silicon oil and its use for the fabrication of timolol voltammetric sensor. Mater Sci Eng C 77:300–307. https://doi.org/10.1016/j.msec.2017.03.168

    Article  CAS  Google Scholar 

  24. Morales GR, Silva TR, Galicia L (2003) Carbon paste electrodes electrochemically modified with cyclodextrin. J Solid State Electrochem 7:355–360

    Article  CAS  Google Scholar 

  25. Alizadeh T, Jamshidi F (2015) Synthesis of nanosized sulfate-modified α-Fe2O3 and its use for the fabrication of all-solid-state carbon paste pH sensor. J Solid State Electrochem 19(4):1053–1062. https://doi.org/10.1007/s10008-014-2716-4

    Article  CAS  Google Scholar 

  26. Tsuji E, Imanishi A, Fukui K, Nakato Y (2011) Electrocatalytic activity of amorphous RuO2 electrode for oxygen evolution in an aqueous solution. Electrochim Acta 56(5):2009–2016. https://doi.org/10.1016/j.electacta.2010.11.062

    Article  CAS  Google Scholar 

  27. Das D, Sen PK, Das K (2008) Mechanism of potentiostatic deposition of MnO2 and electrochemical characteristics of the deposit in relation to carbohydrate oxidation. Electrochim Acta 54(2):289–295. https://doi.org/10.1016/j.electacta.2008.07.082

    Article  CAS  Google Scholar 

  28. Sun W, Wang X, Wang W, Lu Y, Xi J, Zheng W, Wu F, Ao H, Li G (2015) Electrochemical DNA sensor for Staphylococcus aureus nuc gene sequence with zirconia and graphene modified electrode. J Solid State Electrochem 19(8):2431–2438. https://doi.org/10.1007/s10008-015-2893-9

    Article  CAS  Google Scholar 

  29. Guerrini E, Vallini S, Colombo A, Trasatti SP, Trasatti S (2014) Anodic films containing zirconia nanoparticles for corrosion protection of AA1050 aluminum alloy. J Solid State Electrochem 18(5):1457–1468. https://doi.org/10.1007/s10008-013-2274-1

    Article  CAS  Google Scholar 

  30. Zhao YH, Du QQ, Cao XF, Chi B, Zhang J, Zhang CM, Liu T, Wang XJ, Su YG (2012) Electronic structure and electrocatalytic activity of cerium-doped tantalum oxide. J Electroanal Chem 681:139–143. https://doi.org/10.1016/j.jelechem.2012.06.003

    Article  CAS  Google Scholar 

  31. Doménech A, Aucejo R, Alarcón J, Navarro P (2004) Electrocatalysis of the oxidation of methylene dioxyamphetamines at electrodes modified with cerium-doped zirconias. Electrochem Commun 6(7):719–723. https://doi.org/10.1016/j.elecom.2004.05.013

    Article  CAS  Google Scholar 

  32. Chen CH, Chiou YJ, Liou WJ, Lin WS, Lin HM, Wu SH (2011) Synthesis and electrocatalysis application of hybrid platinum/cerium oxide/multi-walled carbon nanotubes. Funct Mater Lett 4(03):295–298. https://doi.org/10.1142/S1793604711002032

    Article  CAS  Google Scholar 

  33. Duan T, Chen Y, Wen Q, Duan Y (2015) Different mechanisms and electrocatalytic activities of Ce ion or CeO2 modified Ti/Sb–SnO2 electrodes fabricated by one-step pulse electrocodeposition. RSC Adv 5(25):19601–19612. https://doi.org/10.1039/C5RA01876E

    Article  CAS  Google Scholar 

  34. Feng JX, Ye SH, Xu H, Tong YX, Li GR (2016) Design and synthesis of FeOOH/CeO2 heterolayered nanotube electrocatalysts for the oxygen evolution reaction. Adv Mater 28(23):4698–4703. https://doi.org/10.1002/adma.201600054

    Article  CAS  PubMed  Google Scholar 

  35. Esch F, Fabris S, Zhou L, Montini T, Africh C, Fornasiero P, Comelli G, Rosei R (2005) Electron localization determines defect formation on ceria substrates. Science 309(5735):752–755. https://doi.org/10.1126/science.1111568

    Article  CAS  PubMed  Google Scholar 

  36. Porter DL, Evans AG, Heuer AH (1979) Transformation-toughening in partially-stabilized zirconia (PSZ). Acta Met 27(10):1649–1654. https://doi.org/10.1016/0001-6160(79)90046-4

    Article  CAS  Google Scholar 

  37. Chang JP, Lin YS, Chu K (2001) Rapid thermal chemical vapor deposition of zirconium oxide for metal-oxide-semiconductor field effect transistor application. J Vacuum Sci Tech B 19(5):1782–1787. https://doi.org/10.1116/1.1396639

    Article  CAS  Google Scholar 

  38. Doménech A, Alarcón J (2007) Microheterogeneous electrocatalytic chiral recognition at monoclinic vanadium-doped zirconias: enantioselective detection of glucose. Anal Chem 79(17):6742–6751. https://doi.org/10.1021/ac070623w

    Article  CAS  PubMed  Google Scholar 

  39. Tekeli S, Kayış A, Gürü M (2008) Microstructural, mechanical and electrical properties of alumina-doped cubic zirconia (c-ZrO2). J Solid State Electrochem 12(7-8):791–797. https://doi.org/10.1007/s10008-008-0530-6

    Article  CAS  Google Scholar 

  40. Doménech A, Montoya N, Alarcón J (2012) Electrochemical characterization of praseodymium centers in PrxZr1−xO2 zirconias using electrocatalysis and photoelectrocatalysis. J Solid State Electrochem 16(3):963–975. https://doi.org/10.1007/s10008-011-1470-0

    Article  CAS  Google Scholar 

  41. Alizadeh T, Hamidia N, Ganjali MR, Nourozi P (2017) Development of a highly selective and sensitive electrochemical sensor for Bi3+determination based on nano-structured bismuth-imprinted polymer modified carbon/carbon nanotube paste electrode. Sensors Actuators B Chem 245:605–614. https://doi.org/10.1016/j.snb.2017.02.024

    Article  CAS  Google Scholar 

  42. Alizadeh T (2012) Application of electrochemical impedance spectroscopy and conventional rebinding experiments for the investigation of recognition characteristic of bulky and nano-sized imprinted polymers. Mater Chem Phys 135(2-3):1012–1023. https://doi.org/10.1016/j.matchemphys.2012.06.007

    Article  CAS  Google Scholar 

  43. Alizadeha T, Mirzagholipur S (2015) An outstandingly sensitive enzyme-free glucose sensor prepared by co-deposition of nano-sized cupric oxide and multi-walled carbon nanotubes on glassy carbon electrode. Biochem Eng J 97:81–91. https://doi.org/10.1016/j.bej.2015.02.011

    Article  CAS  Google Scholar 

  44. Doménech A, Torres FJ, Alarcón J (2004) Electrochemistry of vanadium-doped ZrSiO4 site-selective electrocatalytic effect on nitrite oxidation. Electrochim Acta 49:4623–4632

    Google Scholar 

  45. Torriero AAJ, Lucoa JM, Sereno L, Rabaa J (2004) Voltammetric determination of salicylic acid in pharmaceuticals formulations of acetylsalicylic acid. Talanta 62(2):247–254. https://doi.org/10.1016/j.talanta.2003.07.005

    Article  CAS  PubMed  Google Scholar 

  46. Neumayr M, Frxednch O, Sontag G, Plttner F (1993) Flow-injection analysis with electrochemical detection for determination of salicylic acid in pharmaceutical preparations. Anal Chim Acta 273:469–475

    Article  CAS  Google Scholar 

  47. Zhang WD, Xu B, Hong YX, Yu YX, Ye JS, Zhang JQ (2010) Electrochemical oxidation of salicylic acid at well-aligned multiwalled carbon nanotube electrode and its detection. J Solid State Electrochem 14(9):1713–1718. https://doi.org/10.1007/s10008-010-1014-z

    Article  CAS  Google Scholar 

  48. Kubota LT, Milagres BG, Gouvea F, Neto GO (1996) A modified carbon paste electrode with silica gel coated with Meldola’s blue and salicylate hydroxylase as a biosensor for salicylate. Anal Lett 29(6):893–910. https://doi.org/10.1080/00032719608001442

    Article  CAS  Google Scholar 

  49. Gualandi I, Scavetta E, Zappoli S, Tonelli D (2011) Electrocatalytic oxidation of salicylic acid by a cobalt hydrotalcite-like compound modified Pt electrode. Biosens Bioelectron 26(7):3200–3206. https://doi.org/10.1016/j.bios.2010.12.026

    Article  CAS  PubMed  Google Scholar 

  50. Petrek J, Havel L, Petrlova J, Adam V, Potesil D, Babula P, Kizek R (2007) Analysis of salicylic acid in willow barks and branches by an electrochemical method. Russ J Plant Physiol 54(4):553–558. https://doi.org/10.1134/S1021443707040188

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Taher Alizadeh.

Electronic supplementary material

ESM 1

(DOCX 31 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Alizadeh, T., Nayeri, S. Electrocatalytic oxidation of salicylic acid at a carbon paste electrode impregnated with cerium-doped zirconium oxide nanoparticles as a new sensing approach for salicylic acid determination. J Solid State Electrochem 22, 2039–2048 (2018). https://doi.org/10.1007/s10008-018-3907-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-018-3907-1

Keywords

Navigation