Vitamin B12 Plus Graphene Based Bio-Electrocatalyst for Electroreduction of Halocarbons in 1-Butyl-3-Methylimidazolium Tetrafluoroborate: A Special Use of the Synergism between Graphene, Ionic Liquid and Vitamin B12

 Sarwar Ahmad Pandit Sarwar Ahmad Pandit , Mudasir Ahmad Rather Mudasir Ahmad Rather , Sajad Ahmad Bhat Sajad Ahmad Bhat , Pravin P. Ingole Pravin P. Ingole , Mohsin Ahmad Bhat Mohsin Ahmad Bhat
Российский электрохимический журнал
Abstract / Full Text

A bio-functional composite of vitamin B12 with graphene and ionic liquid in chitosan solution was prepared for the first time. The composite was tested for its spectroscopic and electrochemical signatures, which establish the presence of vitamin B12 in its native structure, with its Co-metal centre accessible for heterogeneous electron transfer. Our electrochemical investigations establish that with 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) as electrolyte, the Co(III) metal centre of the biocomposite film can be reduced to electrocatalytically active Co(I) at potentials that are significantly less negative than that reported for solution phase vitamin B12. The biocomposite modified electrode was observed to exhibit excellent electrocatalytic activity toward the electroreduction of halocarbons viz. benzyl bromide, dibromoethane and trichloroacetic acid. The presented investigations indicate that the biocomposite modified electrode minimizes the probability for undesired solution phase reactions of electrogenerated reactive intermediates during electroreduction of dihaloalkanes. This feature is expected to have profound implications on product profile/yield for selective electroreductive reactions of dihaloalkanes. Our comparative electrocatalytic activity investigations for the chosen halocarbons suggest a synergistic activity of the components employed for the fabrication of the biocomposite modified electrode.

Author information
  • Department of Chemistry, University of Kashmir, Hazratbal Srinagar, Jammu and Kashmir, India

    Sarwar Ahmad Pandit, Mudasir Ahmad Rather, Sajad Ahmad Bhat & Mohsin Ahmad Bhat

  • Department of Chemistry, Indian Institute of Technology Delhi, 110016, New Delhi, India

    Pravin P. Ingole

  1. Peters, D.G., McGuire, C.M., Pasciak, E.M., Pe-verly, A.A., Strawsine, L.M., Wagoner, E.R., and Barnes, J.T., Electrochemical dehalogenation of organic pollutants, J. Mex. Chem. Soc., 2014, vol. 58, p. 287.
  2. Wirtz, M., Klucik, J., and Rivera, M., Ferredoxin-mediated electrocatalytic dehalogenation of haloalkanes by cytochrome P450cam, J. Am. Chem. Soc., 2000, vol. 122, p. 1047.
  3. Zhang, Q., Qiao, Y., Hao, F., Zhang, L., Wu, S., Li, Y., Li, J., and Song, X.M., Fabrication of a biocompatible and conductive platform based on a single-stranded DNA/graphene nanocomposite for direct electrochemistry and electrocatalysis, Chem. Eur. J., 2010, vol. 16, p. 8133.
  4. Armand, M., Endres, F., MacFarlane, D.R., Ohno, H., and Scrosati, B., Ionic liquid materials for the electrochemical challenges of the future, Nat. Mater., 2009, vol. 8, p. 621.
  5. Ohno, H., Electrochemical Aspects of Ionic Liquids, 2nd ed., John Wiley & Sons, 2011.
  6. Pandit, S.A., Rather, M.A., Bhat, S.A., Khan, K.Z., Ingole, P.P., and Bhat, M.A., Ionic liquid induced enhancement in the stickiness of sticky dissociative electroreductive C–Cl bond cleavage: a key to eco-green detoxification of chloroacetonitrile, Electrochim. Acta, 2016, vol. 222, p. 1128.
  7. Pratt, D.A. and van der Donk, W.A., On the role of alkylcobalamins in the vitamin B12-catalyzed reductive dehalogenation of perchloroethylene and trichloroethylene, Chem. Commun., 2006, no. 5, p. 558.
  8. Cheng, W. and Compton, R.G., Quantifying the electrocatalytic turnover of vitamin B12-mediated dehalogenation on single soft nanoparticles, Angew. Chem., 2016, vol. 128, p. 1.
  9. Lagunas, M.C., Silvester, D.S., Aldous, L., and Compton, R.G., The electrochemistry of vitamin B12 in ionic liquids and its use in the electrocatalytic reduction of vicinal dibromoalkanes, Electroanalysis, 2006, vol. 18, p. 2263.
  10. Hisaeda, Y., Nishioka, T., Inoue, Y., Asada, K., and Hayashi, T., Electrochemical reactions mediated by vitamin B12 derivatives in organic solvents, Coord. Chem. Rev., 2000, vol. 198, p. 21.
  11. Wang, T., Wang, L., Tu, J., Xiong, H., and Wang, S., Direct electrochemistry and electrocatalysis of heme proteins immobilised in carbon-coated nickel magnetic nanoparticle–chitosan–dimethylformamide composite films in room-temperature ionic liquids, Bioelectrochemistry, 2013, vol. 94, p. 94.
  12. Xu, Y., Cao, M., Liu, H., Zong, X., Kong, N., Zhang, J., and Liu, J., Electron transfer study on graphene modified glassy carbon substrate via electrochemical reduction and the application for tris(2,2′-bipyridyl)ruthenium(II) electrochemiluminescence sensor fabrication, Talanta, 2015, vol. 139, p. 6.
  13. Zhong, X., Yuan, R., and Chai, Y.Q., Synthesis of chitosan-Prussian blue-graphene composite nanosheets for electrochemical detection of glucose based on pseudobienzyme channelling, Sens. Actuators B, 2012, vol. 162, p. 334.
  14. Guo, C.X., Lu, Z.S., Lei, Y., and Li, C.M., Ionic liquid–graphene composite for ultrarace explosive trinitrotoluene detection, Electrochem. Commun., 2010, vol. 12, p. 1237.
  15. Dupont, J., Consorti, C.S., Suarez, P.A.Z., and de Souza, R.F., Preparation of 1-butyl-3-methyl imidazolium-based room temperature ionic liquids, Org. Synth., 1999, vol. 79, p. 236.
  16. Rather, M.A., Rather, G.M., Pandit, S.A., Bhat, S.A., Khan, K.Z., and Bhat, M.A., Ionic liquids: additives for manipulating the nucleophilicity, J. Solution Chem., 2015, vol. 44, p. 1518.
  17. Jan, R., Rather, G.M., and Bhat, M.A., Effect of cosolvent on bulk and interfacial characteristics of imidazolium based room temperature ionic liquids, J. Mol. Liq., 2013, vol. 181, p. 142.
  18. Li, J., Feng, H., Li, J., Jiang, J., Feng, Y., He, L., and Qian, D., Bimetallic Ag–Pd nanoparticles-decorated graphene oxide: a fascinating three-dimensional nanohybrid as an efficient electrochemical sensing platform for vanillin determination, Electrochim. Acta, 2015, vol. 176, p. 827.
  19. Bhat, S.A., Rather, M.A., Pandit, S.A., Ingole, P.P., and Bhat, M.A., Oxides in silver–graphene nanocomposites: electrochemical signatures and electrocatalytic implications, Analyst, 2015, vol. 140, p. 5601.
  20. Lu, X., Hu, J., Yao, X., Wang, Z., and Li, J., Composite system based on chitosan and room-temperature ionic liquid: direct electrochemistry and electrocatalysis of hemoglobin, Biomacromolecules, 2006, vol. 7, p. 975.
  21. Wang, S.F., Chen, T., Zhang, Z.L., Shen, X.C., Lu, Z.X., Pang, D.W., and Wong, K.Y., Direct electrochemistry and electrocatalysis of heme proteins entrapped in agarose hydrogel films in room-temperature ionic liquids, Langmuir, 2005, vol. 21, p. 9260.
  22. Lexa, D. and Saveant, J.M., Electrochemistry of vitamin B12, Acc. Chem. Res., 1983, vol. 16, p. 235.
  23. Lexa, D., Saveant, J.M., and Zickler, J., Electrochemistry of vitamin B12. 5. Cyanocobalamins, J. Am. Chem. Soc., 1980, vol. 102, p. 2654.
  24. Giedyk, M., Shimakoshi, H., Goliszewska, K., Gryko, D., and Hisaeda, Y., Electrochemistry and catalytic propertiesof amphiphilic vitamin B12 derivatives in nonaqueous media, Dalton Tran., 2016, vol. 45, p. 8 340.
  25. Ananthi, A. and Phani, K.L., Self-assembly of gold nanoparticles on sulphide functionalized polydopamine in application to electrocatalytic oxidation of nitric oxide, J. Electroanal. Chem., 2016, vol. 764, p. 7.
  26. Umasankar, Y., Huang, T.Y., and Chen, S.M., Vitamin B12 incorporated with multiwalled carbon nanotube composite film for the determination of hydrazine, Anal. Biochem., 2011, vol. 408, p. 297.
  27. Laviron, E., The use of linear potential sweep voltammetry and of a.c. voltammetry for the study of the surface electrochemical reaction of strongly adsorbed systems and of redox modified electrodes, J. Electroanal. Chem., 1979, vol. 100, p. 263.
  28. Shi, F., Gong, S., Xu, L., Zhu, H., Sun, Z., and Sun, W., Application of graphene–ionic liquid–chitosan composite-modified carbon molecular wire electrode for the sensitive determination of adenosine-5′-monophosphate, Mater. Sci. Eng. C, 2013, vol. 33, p. 4527.
  29. Kang, X., Wang, J., Wu, H., Aksay, I.A., Liu, J., and Lin, Y., Glucose oxidase–graphene–chitosan modified electrode for direct electrochemistry and glucose sensing, Bios. Bioelectron., 2009, vol. 25, p. 901.
  30. Zhu, Z., Li, X., Zeng, Y., Sun, W., Zhu, W., and Huang, X., Application of cobalt oxide nanoflower for direct electrochemistry and electrocatalysis of hemoglobin with ionic liquid as enhancer, J. Phys. Chem. C, 2011, vol. 115, p. 12547.
  31. Roushani, M. and Valipour, A., Using electrochemical oxidation of Rutin in modelling a novel and sensitive immunosensor based on Pt nanoparticle and graphene–ionic liquid–chitosan nanocomposite to detect human chorionic gonadotropin, Sens. Actuators B, 2016, vol. 222, p. 1103.
  32. Bard, A.J. and Faulkner, L.R., Electrochemical Methods. Fundamentals and Applications, 2nd ed., New York: John Wiley and Sons, 2001
  33. Bhat, M.A., Konar, A., Ingole, P.P., and Pandith, A.H., Unusual aspects of ion-pairing effects in room temperature ionic liquids, J. Phys. Org. Chem., 2012, vol. 25, p. 1243.
  34. Lane, G.H., Electrochemical reduction mechanisms and stabilities of some cation types used in ionic liquids and other organic salts, Electrochim. Acta, 2012, vol. 83, p. 513.
  35. Jabbar, M.A., Shimakoshi, H., and Hisaeda, Y., Enhanced reactivity of hydrophobic vitamin B12 towards the dechlorination of DDT in ionic liquid, Chem. Commun., 2007, vol. 16, no. 16, p. 1653.
  36. Zhang, S., Dokko, K., and Watanabe, M., Carbon materialization of ionic liquids: from solvents to materials, Mater. Horiz., 2015, vol. 2, p. 168.
  37. Davies, T.J., Garner, A.C., Davies, S.G., and Compton, R.G., Cyclic voltammetry at microdroplet modified electrodes. A comparison of the reaction of vicinal dibromides with vitamin B12s at the liquid/liquid interface with the corresponding homogeneous process: evidence for polar-solvent effects at the liquid/liquid interface, J. Electoanal. Chem., 2004, vol. 570, p. 171.
  38. Zhou, D., Carrero, H., and Rusling, J.F., Radical vs. anionic pathway in mediated electrochemical reduction of benzyl bromide in a bicontinuous microemulsion, Langmuir, 1996, vol. 12, p. 3067.
  39. Connors, T.F., Arena, J.V., and Rusling, J.F., Electrocatalytic reduction of vicinal dibromides by vitamin B12, J. Phys. Chem., 1988, vol. 92, p. 2810.
  40. Tu, W., Lei, J., and Ju, H., Functionalization of carbon nanotubes with water–insoluble porphyrin in ionic liquid: direct electrochemistry and highly sensitive amperometric biosensing for trichloroacetic acid, Chem. Eur. J., 2009, vol. 15, p. 779.
  41. Su, Y.Z., Fu, Y.C., Wei, Y.M., Yan, J.W., and Mao, B.W., The electrode/ionic liquid interface: electric double layer and metal electrodeposition, ChemPhysChem, 2010, vol. 11, p. 2764.
  42. Ordaz, A.A. and Bedioui, F., The electrocatalytic reduction of organohalides by myoglobin and hemoglobin in a biomembrane-like film and its application to the electrochemical detection of pollutants: new trends and discussion, Sens. Actuators B, 1999, vol. 59, p. 128.
  43. Rusling, J.F., Miaw, C.L., and Couture, E.C., Electrocatalytic dehalogenation of alpha-haloacetic acids by vitamin B12, Inorg. Chem., 1990, vol. 29, p. 2025.
  44. Gaillon, L. and Bediou, F., Voltammetric analysis of the catalytic reactivity of electrogenerated Co(I)–salen with organohalogenated derivatives in an ionic liquid at room temperature, J. Mol. Catal. A: Chem., 2004, vol. 214, p. 91.
  45. Hu, N., Direct electrochemistry of redox proteins or enzymes at various film electrodes and their possible applications in monitoring some pollutants, Pure Appl. Chem., 2001, vol. 73, p. 1979.