Effect of solution composition on the desorption behavior of self-assembled monolayers of alkanethiols with different terminal groups

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription Access

Abstract

Voltammetry and chronoamperometry are used to study the effect of the composition of a solution on the desorption behavior of self-assembled monolayers (SAMs) of alkanethiols with approximately the same chain length but different end groups of thiols (R: –CH3, –CH2OH, and –NH2). The hydrophilic properties of terminal groups for the studied thiols increase in the –CH3 << –NH2 ≤ –CH2OH series. It has been found that the anion and cation compositions of electrolyte significantly affect the electrochemical stability and blocking ability of SAMs of thiols with different terminal groups. It has been established that the electrochemical stability and blocking ability of SAMs decrease in the Li+, Na+, K+ series in basic solutions regardless of the thiol terminal group. The cation nature in perchlorate and chloride solutions is manifested only for thiol with terminal group-NH2. The shape of cathode voltammograms changes for this thiol when passing from basic to ClO4– and Сl– medium, possibly owing to a change in the degree of protonation of the amino group.

Full Text

Restricted Access

About the authors

S. N. Ovchinnikova

Institute of Solid State Chemistry and Mechanochemistry of the Siberian Branch of the Russian Academy of Sciences

Author for correspondence.
Email: ovchin@solid.nsc.ru
Russian Federation, Novosibirsk

T. P. Aleksandrova

Institute of Solid State Chemistry and Mechanochemistry of the Siberian Branch of the Russian Academy of Sciences; Novosibirsk State Technical University

Email: taleks99@mail.ru
Russian Federation, Novosibirsk; K. Marx ave., 20, Novosibirsk, 630073

References

  1. Galbiati, M., Barraud, C., Tatay, S., Bouzehouane, K., Deranlot, C., Jacquet, E., Fert, A., Seneor, P., Mattana, R., and Petroff, F., Unveiling self-assembled monolayers’ potential for molecular spintronics: spin transport at high voltage, Adv. Mater., 2012, vol. 24, p. 6429.
  2. Gooding, J.J., Mearns, F., Yang, W., and Liu, Self-assembled monolayers into the 21(st) century: recent advances and applications, Electroanalysis, 2003, vol. 15, p. 81.
  3. Porter, M.D., Bright, T.B., Allara, D.L., and Chidsey, C.E.D., Spontaneously Organized Molecular Assemblies. 4. Structural Characterization of N-Alkyl Thiol Monolayers on Gold by Optical Ellipsometry, Infrared Spectroscopy, and Electrochemistry, J. Amer. Chem. Soc., 1987, vol. 109, p. 3559.
  4. Boubour, E. and Lennox, R.B., Potential-induced defects in N-alkanethiol self-assembled monolayers monitored by impedance spectroscopy, J. Phys. Chem. B, 2000, vol. 104, p. 9004.
  5. O’Brien, B., Sahalov, H., and Searson, P.C., The temperature dependence of the impedance of alkanethiol self-assembled monolayers, Appl. Phys. Lett., 2010, vol. 97, p. 043110.
  6. Boubour, E. and Lennox, R.B., Stability of Ω-functionalized self-assembled monolayers as a function of applied potential, Langmuir, 2000, vol. 16, p. 7464.
  7. Dai, J., Li, Z., Jin, J., Cheng, J., Kong, J., and Bi, S., Some thought on the existence of ion and water channels in highly dense and well-ordered CH3-terminated alkanethiol self-assembled monolayers on gold, Biosensors and Bioelectronics, 2009, vol. 24, p. 1074. https://doi.org/10.1016/j.bios.2008.08.034
  8. Chavez, M., Sanchez-Obrero, G., Madueno, R., Sevilla, J.M., Blazquez, M., and Pineda, T., Self-assembled monolayers of O-(2-mercaptoethyl)-O-methyl-hexa(ethyleneglycol) on gold electrodes. Effects yhe nature of solution/electrolyte on formation and electron transfer blocking characteristics, J. Electroanal. Chem., 2022, vol. 914, p. 116303. https://doi.org/10.1016/j.jelchem.2022.116303
  9. Sahalov, H., O’Brien, B., Stebe, K.J., Hristova, K., and Searson, P.C., Influence of applied potential on the impedance of alkanethiol Sams, Langmuir, 2007, vol. 23, p. 9681.
  10. Marmisolle, W.A., Capdevila, D.A., Llave, E., Willams, F.J., and Murgida, D.H., Self-assembled monolayers of NH2-terminated thiolates: order, pKa, and specific adsorption, Langmuir, 2013, vol. 29, p.5351. https://doi.org/10.1021/la304730q
  11. Azzaroni, O., Vela, M.E., Martin, H., Fernandez Creus, A., Andreasen, G., and Salvarezza, R.C., Electrodesorption kinetics and molecular interactions at negatively charged self-assembled thiol monolayers in electrolyte solutions, Langmuir, 2001, vol. 17, p. 6647. https://doi.org/10.1021/la010019v
  12. Calvente, J.J., Lopez-Peres, G., and Ramirez, P., Experimental study of the interplay between long-range electron transfer and redox probe permeation at self-assembled monolayers: evidence for potential-induced ion gating, J. Amer. Chem. Soc., 2005, vol. 127, p. 6476.
  13. Li, J., Liang, K.S., Scoles, G., and Ulman, A., Counterion overlayers at the interface between an electrolyte and an ω-functionalized monolayer self-assembled on gold. An X-ray reflectivity study, Langmuir, 1995, vol. 11, p. 4418.
  14. Овчинникова, С.Н. Сравнительное электрохимическое изучение самоорганизации октантиола из водного и водно-этанольного растворов на золотом электроде. Электрохимия. 2016. Т. 52. С. 301. [Ovchinnikova, S.N., Comparative electrochemical study of self-assembly of octanthiol from aqueous and aqueous ethanol solutions on a gold electrode, Russ. J. Electrochem., 2016, vol. 52, p. 260.]
  15. Ovchinnikova, S. and Aleksandrova, T., Influence of the alkanethiol terminal group nature on the electrochemical stability and blocking ability of self-assembled nanofilms on Au electrode, MATEC Web of Conferences, 2021, vol. 340, p. 01013.
  16. Зелинский, А.Г., Бек, Р.Ю. Твердый электрод с обновляемой путем среза поверхностью. Электрохимия. 1985. Т. 21. С. 66. [Zelinskii, A.G. and Beck, R.Yu., Solid electrode with shear-renewable surface, Electrokhimyia (in Russian), 1985, vol. 21. p. 66.]
  17. Клетеник, Ю.Б., Александрова, Т.П. Субмикронная регенерация поверхности твердых индикаторных электродов. Металлические электроды. Журн. аналит. химии. 1997. Т.52. С.752. [Kletenik, Yu.B. and Aleksandrova, T.P., Submicron regeneration of the surface of solid indicator electrodes. Metal electrodes, Zh. Anal. Khim. (in Russian), 1997, vol. 52, p.752.]
  18. Мичри, А.А., Пшеничников, А.Г., Бурштейн, Р.Х. Определение истинной поверхности гладких золотых электродов. Электрохимия. 1972. Т. 8. С. 364. [Michri, A.A., Pshenichnikov, A.G., and Byrshtein, R.Kh., Determination of the true surface of smooth gold electrodes, Electrokhimiya (in Russian), 1972, vol. 8, p. 364.]
  19. Рогожников, Н.А., Бек, Р.Ю. Емкость двойного слоя и потенциал нулевого заряда золотого электрода в цианистых растворах. Электрохимия. 1987. Т. 23. С. 1440. [Rogozhnikov, N.A. and Beck, R.Yu., Double layer capacitance and zero charge potential of a gold electrode in cyanide solutions, Electrokhimiya (in Russian), 1987, vol. 23, p. 1440.]
  20. Wong, S.S. and Porter, M.D., Origin of the multiple voltammetric desorption waves of long-chain alkanthiolate monolayers chemisorbed on annealed gold electrodes, J. Electroanal. Chem., 2000, vol. 485, p. 135.
  21. Love, J.C., Estroff, L.A., Kriebel, J.K., Nuzzo, R.G., and Whitesides, G.M., Self-assembled monolayers of thiolates on metals as a form of nanotechnology, Chem. Rev., 2005, vol. 105, p. 1103.
  22. Iost, R.M. and Crespilho, F.N., Layer-by-layer self-assembly and electrochemistry: applications in biosensing and bioelectronics, Biosensors and Bioelectronics, 2012, vol. 31, p. 1.
  23. Gooding, J.J. and Ciampi, S., The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assembles, Chem. Soc. Rev., 2011, vol. 40, p. 2704.
  24. Chaki, N.R. and Vijayamohanan, K., Self-assembled monolayers as a tunable platform for biosensor applications, Biosensors and Bioelectronics, 2002, vol. 17, p. 1.
  25. Blake, J. and Raj, M., Regeneration of Gold Surfaces Covered by Adsorbed Thiols and Proteins Using Liquid-Phase Hydrogen Peroxide-Mediated UV-Photooxidation, J. Phys. Chem. C, 2013, vol. 117, p. 1335.
  26. Carvalhal, R.F., Freire, R.S., and Kubota, L.T., Polycrystalline Gold Electrodes: A Comparative Study of Pretreatment Procedures Used for Cleaning and Thiol Self-Assembly Monolayer Formation, Electroanalysis, 2005, vol. 17, p. 1251.
  27. Yang, D., Wilde, C.P., and Morin, M., Electrochemical desorption and adsorption of nonyl mercaptan at gold single electrode surfaces, Langmuir, 1996, vol. 12, p. 6570.
  28. Walczak, M.M., Aves, C.A., Lamp, B.D., and Porter, M.D., Electrochemical and X-ray photoelectron spectroscopic evidence for differences in the binding sites of alkanethiolate monolayers chemisorbed at gold, J. Electroanal. Chem., 1995, vol. 396, p. 103.
  29. Muglari, M.I., Erbe, A., Chen, Y., Barth, C., Koelsch, P., and Rohwerder, M., Modulation of electrochemical hydrogen evolution rare by araliphatic thiol monolayers on gold, Electrochim. Acta, 2013, vol. 90, p. 17.
  30. Kislenko, S.A., Nikitina, V.A., and Nazmutdinov, R.R., A molecular dynamics study of the ionic and molecular permeability of alkanethiol monolayers on the gold electrode surface, High energy Chem., 2015, vol. 49, p. 341. https://doi.org/10.1134/S0018143915050069
  31. Лурье, Ю.Ю. Справочник по аналитической химии. М.: Химия, 1979. 480 c. [Lur’e, Yu.Yu., Handbook of Analytical Chemistry (in Russian), Moscow: Khimiya, 1979. 480 p.]
  32. Бек, Р.Ю., Махнырь, Н.В., Зелинский, А.Г. Емкость двойного слоя обновляемого золотого электрода. Электрохимия. 1975. Т. 11. С. 1607. [Beck, R.Yu., Makhnyr’, N.V., and Zelinskii, A.G., Capacitance of electric double-layer at a recoverable gold electrode, Electrochimiya (in Russian), 1975, vol. 11, p. 1503.]
  33. Chen, A. and Lipkowski, J., Electrochemical and spectroscopic studies of hydroxide adsorption at the Au(111) electrode, J. Phys. Chem. B, 1999, vol. 103, p. 682.
  34. Strbac, S. and Adzic, R.R., The influence of OH- chemisorption on the catalytic properties of gold single crystal surfaces for oxygen reduction in alkaline solutions, J. Electroanal. Chem., 1996, vol. 403, p. 169.
  35. Shi, Z. and Lipkowski, J., Chloride adsorption at the Au(111) electrode surface, J. Electroanal. Chem., 1996, vol. 403, р. 225.
  36. Marmisolle, W.A., Capdevila, D.A., Llave, E., Willams, F.J., and Murgida, D.H., Self-assembled monolayers of NH2-terminated thiolates: order, pKa, and specific adsorption, Langmuir, 2013, vol. 29, p. 5351.
  37. Крестов, Г.А. Ионная сольватация, М.: Наука, 1987. 320 с. [Krestov, G.A., Ionic solvation (in Russian), Moscow: Nauka, 1987. 320 p.]

Supplementary files

Supplementary Files
Action
1. JATS XML
Download
2. Fig. 1. Cathodic voltammograms of Au/SAMs electrodes obtained by holding for 120 s at E = −200 mV in a deaerated 0.02 M solution: 1 — LiOH, 2 — NaOH, 3 — KOH in the presence of 0.1 mM thiols with different end groups: –CH3 (a), –CH2OH (b), –NH2 (c).

Download (168KB)
Indexing metadata
3. Fig. 2. Cathodic voltammograms of the Au/SR–NH2 electrode obtained by holding for 120 s at E = −200 mV in a deaerated solution of 0.1 mM thiol + 0.02 M alkaline (a) and perchlorate (b) solution with different cations: 1 — Li+, 2 — Na+, 3 — K+.

Download (110KB)
Indexing metadata
4. Fig. 3. Cathodic voltammograms of the Au/SR–NH2 electrode obtained by keeping it for 120 s in an aerated solution: (a) 0.1 mM thiol and 0.02 M NaOH at different potentials E, V: 1 — (–0.2), 2 — (–0.6), 3 — (–0.7), 4 — (–0.8); (b) 0.1 mM thiol and 0.02 M (NaClO4 + NaOH) at E= –200 mV at different pH of the solution: 1 — 6.0 (0.02 M NaClO4), 2 — 11.2, 3 — 11.9, 4 — 12.3 (0.02 M NaOH).

Download (117KB)
Indexing metadata

Copyright (c) 2024 Russian Academy of Sciences