Chemically modified electrode based on dihexadecyl hydrogen phosphate and carbonaceous materials: improvement of analytical and electrochemical features applied to uranium determination

  • 19 Accesses


This work deals about the evaluation and improvement of analytical and electrochemical features of chemically modified electrode based on dihexadecyl hydrogen phosphate (DPH) and carbonaceous materials. The electrochemical features of films obtained were evaluated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Between the modifications evaluated, the glassy carbon electrode (GCE) modified with CB and DPH (DHP-CB/GCE) showed lower resistance to charge transfer and higher electron transfer rate. Additionally, the highest current of U(VI) was obtained with DHP-CB/GCE in a very stable way, the process present quasi-reversible behavior and it is controlled by a mixture of diffusion and absorption. The best instrumental conditions for U(VI) determination were obtained applying frequency of 15 Hz, amplitude of 100 mV, and deposition potential of − 0.1 V (by square wave cathodic stripping voltammetry). Among the electrolyte compositions (acetate and citrate buffers), ionic strength (from 0.10, 0.15, to 0.20 mol L−1), and pH (from 3.6 to 5.6) evaluated, the highest current of U(VI) were obtained in 0.15 mol L−1 of acetate buffer, pH 5.6. The method was accurate, linear, and sensitive (detection limit of 0.088 μg L−1 using 300 s of deposition).

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

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Subscribe to journal

Immediate online access to all issues from 2019. Subscription will auto renew annually.

US$ 99

This is the net price. Taxes to be calculated in checkout.

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


  1. 1.

    ATSDR (2013) Toxicological profile for uranium. Department of health and human services, Public Health Service, Atlanta

  2. 2.

    Keith LS, Faroon OM, Fowler BA (2007) Uranium. In: Nordberg GF, Fowler BA, Nordberg M, Friberg LT (eds) Handbook on the toxicology of metals, 3rd edn. Academic Press, Burlington, pp 881–903

  3. 3.

    CONAMA (2005) Resolution No. 357/2005. March 17, 2005. Published in DOU no. 053, on march 18, 2005, pages 58-63

  4. 4.

    EPA (2001) Radionuclides rule: a quick reference guide. U.S. Environmental Protection Agency

  5. 5.

    WHO (2012) Uranium in drinking-water: background document for development of WHO guidelines for drinking-water quality. World Health Organization

  6. 6.

    AOAC (2000) Método 993.14 - Trace elements in waters and wastewaters. Inductively coupled plasma-mass spectrometric method

  7. 7.

    APHA (2012) Metals by inductively coupled plasma/mass spectrometry. In: Standard methods for the examination of water and wastewater, 22nd ed. American public health association

  8. 8.

    ASTM (2016) ASTM D5673 - Standard test method for elements in water by inductively coupled plasma—mass spectrometry

  9. 9.

    Khan MH, Warwick P, Evans N (2006) Spectrophotometric determination of uranium with arsenazo-III in perchloric acid. Chemosphere 63(7):1165–1169

  10. 10.

    Yousefi SR, Ahmadi SJ, Shemirani F, Jamali MR, Salavati-Niasari M (2009) Simultaneous extraction and preconcentration of uranium and thorium in aqueous samples by new modified mesoporous silica prior to inductively coupled plasma optical emission spectrometry determination. Talanta 80(1):212–217

  11. 11.

    Santos JS, Teixeira LSG, dos Santos WNL, Lemos VA, Godoy JM, Ferreira SL (2010) Uranium determination using atomic spectrometric techniques: an overview. Anal Chim Acta 674(2):143–156

  12. 12.

    de Oliveira C, Aquino SA, Giacomini GX et al (2019) Uranium determination in industrial effluents by voltammetric method using triazene 1-oxide as an alternative binder. Int J Environ Sci Technol:1–10.

  13. 13.

    Wang J, Lu J, Larson DD, Olsen K (1995) Voltammetric sensor for uranium based on the propyl gallate-modified carbon paste electrode. Electroanalysis 7:247–250

  14. 14.

    Yantasee W, Lin Y, Fryxell GE, Wang Z (2004) Carbon paste electrode modified with carbamoylphosphonic acid functionalized mesoporous silica: a new mercury-free sensor for uranium detection. Electroanalysis 16:870–873

  15. 15.

    Dimovasilis PA, Prodromidis MI (2011) An electrochemical sensor for trace uranium determination based on 6-O-palmitoyl-L-ascorbic acid-modified graphite electrodes. Sensors Actuators B Chem 156:689–694

  16. 16.

    Golikand AN, Asgari M, Maragheh MG, Lohrasbi E (2009) Carbon nanotube-modified glassy carbon electrode for anodic stripping voltammetric detection of Uranyle. J Appl Electrochem 39:65–70

  17. 17.

    Guin SK, Parvathi K, Ambolikar AS et al (2015) An insight into the electrocatalysis of uranyl sulphate on gold nanoparticles modified glassy carbon electrode. Electrochim Acta 154:413–420

  18. 18.

    Nassab HR, Souri A, Javadian A, Amini MK (2015) A novel mercury-free stripping voltammetric sensor for uranium based on electropolymerized N-phenylanthranilic acid film electrode. Sensors Actuators B Chem 215:360–367

  19. 19.

    Ziółkowski R, Górski Ł, Malinowska E (2017) Carboxylated graphene as a sensing material for electrochemical uranyl ion detection. Sensors Actuators B Chem 238:540–547

  20. 20.

    Becker A, Tobias H, Porat Z, Mandler D (2008) Detection of uranium(VI) in aqueous solution by a calix[6]arene modified electrode. J Electroanal Chem 621:214–221

  21. 21.

    Merli D, Protti S, Labò M, Pesavento M, Profumo A (2016) A ω-mercaptoundecylphosphonic acid chemically modified gold electrode for uranium determination in waters in presence of organic matter. Talanta 151:119–125

  22. 22.

    Becker A, Tobias H, Mandler D (2009) Electrochemical determination of uranyl ions using a self-assembled monolayer. Anal Chem 81:8627–8631

  23. 23.

    Shervedani RK, Mozaffari SA (2005) Preparation and electrochemical characterization of a new nanosensor based on self-assembled monolayer of cysteamine functionalized with phosphate groups. Surf Coatings Technol 198:123–128

  24. 24.

    Ziółkowski R, Górski Ł, Oszwałdowski S, Malinowska E (2012) Electrochemical uranyl biosensor with DNA oligonucleotides as receptor layer. Anal Bioanal Chem 402:2259–2266

  25. 25.

    Jarczewska M, Ziółkowski R, Górski Ł, Malinowska E (2014) Electrochemical uranyl cation biosensor with DNA oligonucleotides as receptor layer. Bioelectrochemistry 96:1–6

  26. 26.

    Wu Y, Hu S (2007) Direct electrochemistry of glucose oxidase in a colloid Au–dihexadecylphosphate composite film and its application to develop a glucose biosensor. Bioelectrochemistry 70(2):335–341

  27. 27.

    Wu K, Sun Y, Hu S (2003) Development of an amperometric indole-3-acetic acid sensor based on carbon nanotubes film coated glassy carbon electrode. Sensors Actuators B Chem 96:658–662

  28. 28.

    Sanz-Medel A, Fernandez de la Campa M del R, Gonzalez EB, Fernandez-Sanchez ML (1999) Organised surfactant assemblies in analytical atomic spectrometry. Spectrochim Acta Part B At Spectrosc 54:251–287

  29. 29.

    Ibáñez-Redín G, Silva TA, Vicentini FC, Fatibello-Filho O (2018) Effect of carbon black functionalization on the analytical performance of a tyrosinase biosensor based on glassy carbon electrode modified with dihexadecylphosphate film. Enzym Microb Technol 116:41–47

  30. 30.

    Yao S, Xu J, Wang Y et al (2006) A highly sensitive hydrogen peroxide amperometric sensor based on MnO2 nanoparticles and dihexadecyl hydrogen phosphate composite film. Anal Chim Acta 557:78–84

  31. 31.

    Garcia LLC, Figueiredo-Filho LCS, Oliveira GG et al (2013) Square-wave voltammetric determination of paraquat using a glassy carbon electrode modified with multiwalled carbon nanotubes within a dihexadecylhydrogenphosphate (DHP) film. Sensors Actuators B Chem 181:306–311

  32. 32.

    Geng M, Yang YJ, Hu S et al (2009) The voltammetric determination of phenolphthalein on multi-walled carbon nanotube-DHP composite film-modified glassy carbon electrode. Fullerenes, Nanotub Carbon Nanostructures 17:285–297

  33. 33.

    Deroco PB, Rocha-Filho RC, Fatibello-Filho O (2018) A new and simple method for the simultaneous determination of amoxicillin and nimesulide using carbon black within a dihexadecylphosphate film as electrochemical sensor. Talanta 179:115–123

  34. 34.

    Hu X, Wang P, Yang J, Zhang B, Li J, Luo J, Wu K (2010) Enhanced electrochemical detection of erythromycin based on acetylene black nanoparticles. Colloids Surfaces B Biointerfaces 81(1):27–31

  35. 35.

    Maciel JV, Silva TA, Dias D, Fatibello-Filho O (2018) Electroanalytical determination of eugenol in clove oil by voltammetry of immobilized microdroplets. J Solid State Electrochem 22:2277–2285

  36. 36.

    Noskova GN, Zakharova EA, Kolpakova NA, Kabakaev AS (2012) Electrodeposition and stripping voltammetry of arsenic(III) and arsenic(V) on a carbon black–polyethylene composite electrode in the presence of iron ions. J Solid State Electrochem 16:2459–2472

  37. 37.

    Zhou K, Tian Y, Ma H et al (2018) Photoelectrocatalytic performance of conductive carbon black-modified Ti/F-PbO2 anode for degradation of dye wastewater (reactive brilliant blue KN-R). J Solid State Electrochem 22:1131–1141

  38. 38.

    Zhutaeva GV, Bogdanovskaya VA, Davydova ES et al (2014) Kinetics and mechanism of oxygen electroreduction on Vulcan XC72R carbon black modified by pyrolysis products of cobalt 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrine in a broad pH interval. J Solid State Electrochem 18:1319–1334

  39. 39.

    Maciel JV, Fava EL, Silva TA et al (2017) A combination of voltammetry of immobilized microparticles and carbon black-based crosslinked chitosan films deposited on glassy carbon electrode for the quantification of hydroquinone in dermatologic cream samples. J Solid State Electrochem 21:2859–2868

  40. 40.

    Fu Y, Liu Y, Li Y et al (2015) Synergistic electrocatalysis of N,N′-bis(salicylidene)-ethylenediamine-cobalt(II) and conductive carbon black (BP) for high efficient CO2 electroreduction. J Solid State Electrochem 19:3355–3363

  41. 41.

    Janegitz BC, Marcolino-Junior LH, Campana-Filho SP et al (2009) Anodic stripping voltammetric determination of copper(II) using a functionalized carbon nanotubes paste electrode modified with crosslinked chitosan. Sensors Actuators B Chem 142:260–266

  42. 42.

    Chaisiwamongkhol K, Batchelor-McAuley C, Sokolov SV et al (2017) Optimising carbon electrode materials for adsorptive stripping voltammetry. Appl Mater Today 7:60–66

  43. 43.

    Phillips C, Al-Ahmadi A, Potts S-J et al (2017) The effect of graphite and carbon black ratios on conductive ink performance. J Mater Sci 52:9520–9530

  44. 44.

    Wang F, Hu S (2005) Electrochemical reduction of dioxygen on carbon nanotubes–dihexadecyl phosphate film electrode. J Electroanal Chem 580:68–77

  45. 45.

    Ardila JA, Oliveira G, Medeiros A, Fatibello-filho O (2014) Square-wave adsortive stripping voltammetric determination of nanomolar levels of bezafibrate using a glassy carbon electrode modified with multi-walled carbon nanotubes within a dihexadecyl hydrogen phosphate film. Analyst 139(7):1762–1768

  46. 46.

    Brett CMA, Brett AMO (1993) Electrochemistry: principles, methods and aplication, 1st edn. Oxford Science Publications

  47. 47.

    Domingos JB, Longhinotti E, Machado VG, Nome F (2003) A química dos ésteres de fosfato. Quim Nova 26:745–753

  48. 48.

    Carmona-Ribeiro AM (1990) Dihexadecylphosphate bilayers: interbilayer interactions and intrabilayer structure. J Colloid Interface Sci 139:343–350

  49. 49.

    Tricot Y-M, Furlong DN, Sasse WHF et al (1984) Dihexadecylphosphate vesicle dispersions—preparation, physical properties, and interactions with cationic components used in the solar photolysis of water. J Colloid Interface Sci 97:380–391

  50. 50.

    Djogić R, Branica M (1995) Square-wave cathodic stripping voltammetry of hydrolyzed uranyl species. Anal Chim Acta 305:159–164

  51. 51.

    Martell AE, Smith RM (1977) Critical stability constants. Vol. 3 : Other organic ligands. Plenum Publishing Corporation

  52. 52.

    AOAC (2016) Guidelines for standard method performance requirements (appendix F). In: Official methods of analysis of AOAC International. AOAC International, Gaithersburg

Download references


The authors would like to thank CEME-SUL FURG and SDECT.

Author information

Correspondence to Daiane Dias.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material


(DOCX 832 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

de Araujo Aquino, S., Maciel, J.V. & Dias, D. Chemically modified electrode based on dihexadecyl hydrogen phosphate and carbonaceous materials: improvement of analytical and electrochemical features applied to uranium determination. J Solid State Electrochem (2020).

Download citation


  • Uranium
  • Carbon black
  • Dihexadecyl phosphate
  • Chemically modified electrode
  • Voltammetry