Study of Organic Sulfide Oxidation on the Modified Graphite Electrodes by Co, Fe and Ni Nano Particles

 Ghodsiyeh Sadat Ferdowsi Ghodsiyeh Sadat Ferdowsi, Majid JafarianMajid Jafarian, Saeed RayatiSaeed Rayati, Parinaz NafariehParinaz Nafarieh
Российский электрохимический журнал
Abstract / Full Text

Electro-oxidation of methyl phenyl sulfide with the aim of producing sulfoxide and sulfone was investigated over Ni, Co, Fe, and their alloys on graphite electrodes in the acetic acid as a non-toxic solvent. The modified electrodes were prepared by cyclic voltammetry technique. The surface morphology of electrodes was investigated by scanning electron microscopy and the presence of metal nanoparticles on the graphite was investigated by X-ray diffraction. The catalytic treatment and synergistic effects of the modified electrodes were studied by electrochemical techniques such as cyclic voltammetry (CV) and chronoamperometry (CA). It was found the performance of all the modified electrodes is successful. In the attendance of methyl phenyl sulfide, the graphite/CoFe modified electrode (G/CoFe) showed the highest performance for electro-oxidation also there was a linear relationship between the square root of the scan rate and anodic current in low scan rates, that indicates a diffusion controlled process. The diffusion coefficient, heterogeneous electron transfer rate constant and electron transfer coefficient were determined for methyl phenyl sulfide electrochemical oxidation. Electro-oxidation of methyl phenyl sulfide by electrolysis method was investigated and its results were studied by gas chromatograph (GC). Based on GC studies, the electro-oxidation of methyl phenyl sulfide by electrolysis produced methyl phenyl sulfoxide and methyl phenyl sulfone. Also, a mechanism for electro-oxidation of sulfide was proposed. The using of non-noble metals as the electrocatalyst for the first time for the organic sulfide electro-oxidation, the very easy, affordable and fast preparation of the modified electrode, high performance of the modified electrode, no need of using oxidant and co-catalyst and designing a homogeneous media with proper conductivity for oxidation of insoluble in water compounds demonstrate important items for the use of this procedure and electrode in the subsequent investigation of sulfides.

Author information
  • Department of Chemistry, K.N. Toosi University of Technology, 1541849611, Tehran, Iran Ghodsiyeh Sadat Ferdowsi, Majid Jafarian, Saeed Rayati & Parinaz Nafarieh
  1. Rayati, S., Khodaei, E., Jafarian, M., and Wojtczak, A., Mn-Schiff base complex supported on magnetic nanoparticles: synthesis, crystal structure, electrochemical properties and catalytic activities for oxidation of olefins and sulfides, Polyhedron, 2017, vol. 133, p. 327.
  2. Fareghi-Alamdari, R., Zekri, N., Moghadam, A.J., and Farsani, M.R., Green oxidation of sulfides to sulfoxides and sulfones with H2O2 catalyzed by ionic liquid compounds based on Keplerate polyoxometalates, Catal. Commun., 2017, vol. 98, p. 71.
  3. Paim, L.L. and Stradiotto, N.R., Electrooxidation of sulfide by cobalt pentacyanonitrosylferrate film on glassy carbon electrode by cyclic voltammetry, Electrochim. Acta, 2010, vol. 55, p. 4144.
  4. Miller, B. and Chen, A., Effect of concentration and temperature on electrochemical oscillations during sulfide oxidation on Ti/Ta2O5-IrO2 electrodes, Electrochim. Acta, 2005, vol. 50, p. 2203.
  5. Muñoz, M., Gallo, M.A., Gutiérrez-Alejandre, A., Gazzoli, D., and Cabello, C.I., Molybdenum-containing systems based on natural kaolinite as catalysts for selective oxidation of aromatic sulfides, Appl. Catal. B Environ., 2017, vol. 219, p. 683.
  6. Hristova, E., Mitov, M., Rashkov, R., Arnaudova, M., and Popov, A., Sulphide oxidation on electrodeposited Ni–Mo–W catalysts, Bulg. Chem. Commun., 2008, vol. 40, p. 291.
  7. Abdi, G., Alizadeh, A., and Khodaei, M.M., Highly carboxyl-decorated graphene oxide sheets as metal-free catalytic system for chemoselective oxidation of sulfides to sulfones, Mater. Chem. Phys., 2017, vol. 201, p. 323.
  8. Rayati, S., Nejabat, F., and Zakavi, S., Chemoselective oxidation of sulfides to sulfoxides with urea hydrogen peroxide (UHP) catalyzed by non-, partially and fully β-brominated meso-tetraphenylporphyrinatomanganese(III) acetate, Inorg. Chem. Commun., 2014, vol. 40, p. 82.
  9. Rayati, S. and Nejabat, F., Catalytic activity of Fe-porphyrins grafted on multiwalled carbon nanotubes in the heterogeneous oxidation of sulfides and degradation of phenols in water, Comptes Rendus Chim., 2017, vol. 20, p. 967.
  10. Rafiee, E. and Shahebrahimi, S., Organic-inorganic hybrid polyionic liquid based polyoxometalate as nano porous material for selective oxidation of sulfides, J. Mol. Struct., 2017, vol. 1139, p. 255.
  11. Rayati, S., et al., Ni(II) and V(IV) schiff base complexes derived from 2,2'-dimethylpropandiamine: the crystal structure, electrochemical properties and catalytic activities in oxidation of sulfides, J. Coord. Chem., 2017, vol. 70, p. 1424.
  12. Rayati, S., et al., Cu-schiff base complex grafted onto graphene oxide nanocomposite: synthesis, crystal structure, electrochemical properties and catalytic activity in oxidation of olefins, Inorg. Chim. Acta, 2017, vol. 266, p. 520.
  13. Hammerich, O. and Speiser, B., Organic Electrochemistry: Revised and Expanded (CRC Press, 2015).
  14. Dai, L., Carbon-based catalysts for metal-free electrocatalysis, Curr. Opin. Electrochem., 2017, vol. 4, no. 1, p. 18.
  15. Ferdowsi, G.S., Seyedsadjadi, S.A., and Ghaffarinejad, A., Electroless deposition of the Ni nanoparticles on the graphite electrode for glucose oxidation, Anal. Bioanal. Chem., 2014, vol. 6, no. 4, p. 379.
  16. Lin, Q., Wei, Y., Liu, W., Yu, Y., and Hu, J., Electrocatalytic oxidation of ethylene glycol and glycerol on nickel ion implanted-modified indium tin oxide electrode, Int. J. Hydrogen Energy, 2017, vol. 42, p. 1403.
  17. Petersson, M., Electrocatalytic oxidation of ascorbic acid and voltammetric determination with a ferrocene-modified platinum electrode, Anal. Chim. Acta, 1986, vol. 187, p. 333.
  18. Rostami, T., Jafarian, M., Miandari, S., Mahjani, M.G., and Gobal, F., Synergistic effect of cobalt and copper on a nickel-based modified graphite electrode during methanol electro-oxidation in NaOH solution, Cuihua Xuebao/Chinese J. Catal., 2015, vol. 36, p. 1867.
  19. Ferdowsi, G.S., Seyedsadjadi, S.A., and Ghaffarinejad, A., Ni nanoparticle modified graphite electrode for methanol electrocatalytic oxidation in alkaline media, J. Nanostruct. Chem., 2015, vol. 5, p. 17.
  20. Amin, R.S., Hameed, R.M.A., El-Khatib, K.M., Youssef, M.E., and Elzatahry, A.A., Pt–NiO/C anode electrocatalysts for direct methanol fuel cells, Electrochim. Acta, 2012, vol. 59, p. 499.
  21. Osmieri, L., et al., Fe–N/C catalysts for oxygen reduction reaction supported on different carbonaceous materials. Performance in acidic and alkaline direct alcohol fuel cells, Appl. Catal. B Environ., 2017, vol. 205, p. 637.
  22. Muench, F., et al., Electroless synthesis of nanostructured nickel and nickel-boron tubes and their performance as unsupported ethanol electrooxidation catalysts, J. Power Sources, 2013, vol. 222, p. 243.
  23. Soliman, A.B., Abdel-Samad, H.S., Rehim, S.S.A., Ahmed, M.A., and Hassan, H.H., High performance nano-Ni/graphite electrode for electro-oxidation in direct alkaline ethanol fuel cells, J. Power Sources, 2016, vol. 325, p. 653.
  24. Cuña, A., et al., Electrochemical and spectroelectrochemical analyses of hydrothermal carbon supported nickel electrocatalyst for ethanol electro-oxidation in alkaline medium, Appl. Catal. B Environ., 2017, vol. 202, p. 95.
  25. Xu, Z., et al., Enhanced ethanol electro-oxidation on CeO2-modified Pt/Ni catalysts in alkaline solution, Chin. J. Catal., 2017, vol. 38, p. 305.
  26. Chen, W., Zhang, Y., and Wei, X., Catalytic performances of PdNi/MWCNT for electrooxidations of methanol and ethanol in alkaline media, Int. J. Hydrogen Energy, 2015, vol. 40, p. 1154.
  27. Jongsomjit, S., Prapainainar, P., and Sombatmankhong, K., Synthesis and characterisation of Pd–Ni–Sn electrocatalyst for use in direct ethanol fuel cells, Solid State Ionics, 2016, vol. 288, p. 147.
  28. Jafarian, M., Mirzapoor, A., Danaee, I., Shahnazi, S.A.A., and Gobal, F., A comparative study of the electrooxidation of C1 to C3 aliphatic alcohols on Ni modified graphite electrode, Sci. China Chem., 2012, vol. 55, p. 1819.
  29. Bard, A.J., Faulkner, L.R., Leddy, J., and Zoski, C.G., Electrochemical Methods: Fundamentals and Applications, New York: Wiley, 1980.
  30. Laviron, E., General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems, J. Electroanal. Chem. Interfacial Electrochem., 1979, vol. 101, p. 19.