Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Determination of Reorganization Energy from the Temperature Dependence of Electron Transfer Rate Constant for Hydroquinone-tethered Self-assembled Monolayers (SAMs)

  • Park, Won-choul (ACEN Co., LTD #108A TB1 Center, Hankuk University of Foreign Studies) ;
  • Hong, Hun-Gi (Department of Chemistry Education, Seoul National University)
  • Published : 2006.03.20
Download PDF
⟨ Previous Next ⟩

Abstract

The temperature dependence on the electron transfer rate constant $(k_{app})$ for hydroquinone redox center in $H_2Q(CH_2)_n$SH-SAMs (n = 1, 4, 6, 8, 10, and 12) on gold electrode was investigated to obtain reorganization energy $(\lambda)$ using Laviron’s formalism and Arrhenius plot of ln $[k_{app}/T^{1/2}]$ vs. T^{-1} based on the Marcus densityof-states model. All the symmetry factors measured for the SAMs were relatively close to unity and rarely varied to temperature change as expected. The electron tunneling constant $(\beta)$ determined from the dependence of the $k_{app}$ on the distance between the redox center and the electrode surface gives almost the same $\beta$ values which are quite insensitive to temperature change. Good linear relationship of Arrhenius plot for all $H_2Q(CH_2)_n$SH-SAMs on gold electrode was obtained in the temperature range from 273 to 328 K. The slopes n Arrhenius plot deduced that $\lambda$ of hydroquinone moiety is ca. 1.3-1.4 eV irrespectively of alkyl chain length of the electroactive SAM.

Keywords

References

  1. McLendon, G. Acc. Chem. Res. 1988, 21, 160 https://doi.org/10.1021/ar00148a005
  2. Ulman, A. An Introduction to Ultrathin Organic Films: From Langmuir-Blodgett to Self-Assembly; Academic Press: San Diego, CA, 1991
  3. Murray, R. W. Molecular Design of Electrode Surface; Techniques of Chemistry Series; John Wiley & Sons, Inc.: New York, 1992; Vol. XXII
  4. Finklea, H. O. In Electroanalytical Chemistry; Bard, A. J., Rubinstein, I., Eds.; Marcel Dekker: New York, 1996; Vol 19, p109
  5. Foster, R. J.; Faulkner, L. R. J. Am. Chem. Soc. 1994, 116, 5453 https://doi.org/10.1021/ja00091a058
  6. Tender, L.; Carter, M. T.; Murray, R. W. Anal. Chem. 1994, 66, 3173 https://doi.org/10.1021/ac00091a028
  7. Rowe, G. K.; Carter, M. T.; Richardson, J. N.; Murray, R. W. Langmuir 1995, 11, 1797 https://doi.org/10.1021/la00005a059
  8. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y.-P. J. Phys. Chem. 1995, 99, 13141 https://doi.org/10.1021/j100035a016
  9. Weber, K. S.; Creager, S. E. J. Electroanal. Chem. 1998, 458, 17 https://doi.org/10.1016/S0022-0728(98)00303-9
  10. Curtin, L. S.; Peck, S. R.; Tender, L. M.; Murray, R. W.; Rowe, G. K.; Creager, S. E. Anal. Chem. 1993, 65, 386 https://doi.org/10.1021/ac00052a013
  11. Marcus, R. A. J. Chem. Phys. 1965, 43, 679 https://doi.org/10.1063/1.1696792
  12. Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265 https://doi.org/10.1016/0304-4173(85)90014-X
  13. Hong, H.-G.; Park, W.; Yu, E. Bull. Korean Chem. Soc. 2000, 21, 23
  14. Hong, H.-G.; Park, W. Langmuir 2001, 17, 2483
  15. Hong, H.-G.; Park, W. Bull. Korean Chem. Soc. 2005, 26, 1885 https://doi.org/10.5012/bkcs.2005.26.11.1885
  16. Gobi, K. V.; Okajima, T.; Tokuda, K.; Ohsaka, T. Langmuir 1998, 14, 1108 https://doi.org/10.1021/la970694y
  17. Laviron, E. J. Electroanal. Chem. 1979, 101, 19 https://doi.org/10.1016/S0022-0728(79)80075-3
  18. Bard, A. J.; Faulkner, L. R. Electrochemical Methods; Wiley: New York, 1980
  19. Curtiss, L. A.; Halley, J. W.; Hautman, J.; Hung, N. C.; Nagy, Z.; Rhee, Y. J.; Yonco, R. M. J. Electrochem. Soc. 1991, 138, 2032 https://doi.org/10.1149/1.2085919
  20. Chidsey, C. E. D. Science 1991, 51, 919
  21. Sutin, N. Acc. Chem. Res. 1982, 15, 275 https://doi.org/10.1021/ar00081a002
  22. Finklea, H. O.; Hanshew, D. D. J. Am. Chem. Soc. 1992, 114, 3173 https://doi.org/10.1021/ja00035a001
  23. Marcus, R. A. J. Phys. Chem. 1963, 67, 853 https://doi.org/10.1021/j100798a033
  24. Marcus, R. A. J. Chem. Phys. 1965, 43, 679 https://doi.org/10.1063/1.1696792
  25. Lide, D. R. CRC Handbook of Chemistry and Physics; CRC Press: Boca Raton, FL, 1990

Cited by

  1. An Electrochemical Scanning Tunneling Microscopy Study of 2-(6-Mercaptoalkyl)hydroquinone Molecules on Au(111) vol.132, pp.21, 2010, https://doi.org/10.1021/ja101666q
  2. Step-wise proton-coupled electron transfer extended to aminobenzoquinone modified monolayers vol.13, pp.6, 2011, https://doi.org/10.1039/C0CP01251C
  3. Proton-Coupled Electron Transfer vol.112, pp.7, 2012, https://doi.org/10.1021/cr200177j
  4. Multicopper Models for the Laccase Active Site: Effect of Nuclearity on Electrocatalytic Oxygen Reduction vol.53, pp.16, 2014, https://doi.org/10.1021/ic501080c
  5. Effect of Axial Ligand, Spin State, and Hydrogen Bonding on the Inner-Sphere Reorganization Energies of Functional Models of Cytochrome P450 vol.53, pp.19, 2014, https://doi.org/10.1021/ic501112a
  6. Nanodomains of Juglonethiol on Au(111): Relationship between Domain Size and Electrochemical Properties vol.119, pp.52, 2015, https://doi.org/10.1021/acs.jpcc.5b10324
  7. Quantum–Classical Path Integral Simulation of Ferrocene–Ferrocenium Charge Transfer in Liquid Hexane vol.6, pp.24, 2015, https://doi.org/10.1021/acs.jpclett.5b02265
  8. Studies on electrodeposition behavior of Sn–Bi alloys in plating baths modified by hydroquinone and gelatin vol.51, pp.12, 2016, https://doi.org/10.1007/s10853-016-9883-x
  9. Protein Oligomerization Based on Brønsted Acid Reaction vol.7, pp.4, 2017, https://doi.org/10.1021/acscatal.7b00272
  10. Enzyme Biofuel Cells: Thermodynamics, Kinetics and Challenges in Applicability vol.1, pp.11, 2014, https://doi.org/10.1002/celc.201402141
  11. Observation of two discrete conductivity states in quinone-oligo(phenylene vinylene) vol.21, pp.8, 2010, https://doi.org/10.1088/0957-4484/21/8/085704
  12. Electrocatalytic Behavior of Self-assembled Monolayer of a Novel Tetraazamacrocyclic Copper(II) Complex in Ascorbate Oxidation vol.27, pp.6, 2006, https://doi.org/10.5012/bkcs.2006.27.6.817
  13. Electrochemical Approach to the Mechanistic Study of Proton-Coupled Electron Transfer vol.108, pp.7, 2006, https://doi.org/10.1021/cr068065t
  14. Heterogeneous Proton-Coupled Electron Transfer of an Aminoanthraquinone Self-Assembled Monolayer vol.113, pp.12, 2006, https://doi.org/10.1021/jp807287p
  15. Freestanding three-dimensional graphene foam gives rise to beneficial electrochemical signatures within non-aqueous media vol.1, pp.19, 2006, https://doi.org/10.1039/c3ta10727b
  16. Direct Measurement of Water Permeation in Submerged Alkyl Thiol Self-Assembled Monolayers on Gold Surfaces Revealed by Neutron Reflectometry vol.35, pp.16, 2006, https://doi.org/10.1021/acs.langmuir.9b00541
  17. Contributions to cytochrome c inner- and outer-sphere reorganization energy vol.12, pp.35, 2006, https://doi.org/10.1039/d1sc02865k