Springer Nature is making Coronavirus research free. View research | View latest news | Sign up for updates

Photoreduction of Methylviologen in Saponite Clay: Effect of Methylviologen Adsorption Density on the Reaction Efficiency

  • 5 Accesses

Abstract

To identify the mechanisms for and to estimate the photochemical reaction efficiency of molecules in solid-state host materials is difficult. The objective of the present research was to measure the photogeneration efficiency of the methylviologen cation radical (MV+•) hosted in a semi-transparent hybrid film composed of MV2+ and saponite, a 2:1 clay mineral. MV+• is the one-electron reduced species of MV2+. MV+• was generated by UV irradiation of these films. The fluorescence intensity of MV2+ and the photogeneration efficiency of MV+• depended on the loading level of MV2+. When the loading level of MV2+ was high (75% of the cation exchange capacity (abbreviated as % CEC) of saponite), its fluorescence was reduced considerably because of the self-fluorescence quenching reaction, and the photogeneration efficiency of MV+• was relatively high (quantum yield φ = 3.5×10–2) compared to that of films with low adsorption density (10% CEC, φ = 1.1×10–2). Furthermore, when the loading level of MV2+ was very low (0.13% CEC), a self-fluorescence quenching reaction was not observed and MV+• was not generated. From these observations, one of the principal mechanisms of the self-quenching reaction and MV+• formation in saponite is the electron transfer reaction between excited MV2+ and adjacent MV2+ molecules in the ground state.

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

Fig. 1.
Fig. 2.
Fig. 3.
Fig. 4.
Fig. 5.
Fig. 6.
Fig. 7.

References

  1. Alvaro, M., García, H., García, S., Márquez, F., & Scaiano, J. C. (1997). Intrazeolite photochemistry. 17. Zeolites as electron donors: Photolysis of methylviologen incorporated within zeolites. The Journal of Physical Chemistry B, 101, 3043–3051.

  2. Auerbach, S. M., Carrado, K. A., & Dutta, P. K. (2004). Handbook of Layered Materials, 10. Florida: CRC Press.

  3. Bahnemann, D. W., Fischer, C.-H., Janata, E., & Henglein, A. (1987). The two-electron oxidation of methyl viologen. Detection and analysis of two fluorescing products. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 83, 2559.

  4. Bard, A. J., & Fox, M. A. (2002). Artificial photosynthesis: Solar splitting of water to hydrogen and oxygen. Accounts of Chemical Research, 28, 141–145.

  5. Bockman, T. M., & Kochi, J. K. (1990). Isolation and oxidation-reduction of methylviologen cation radicals. Novel disproportionation in charge-transfer salts by X-ray crystallography. The Journal of Organic Chemistry, 55, 4127–4135.

  6. Chernia, Z., & Gill, D. (1999). Flattening of tmpyp adsorbed on laponite. Evidence in observed and calculated UV−vis spectra. Langmuir, 15, 1625–1633.

  7. Ebbesen, T. W., Manring, L. E., & Peters, K. S. (1984). Picosecond photochemistry of methyl viologen. Journal of the American Chemical Society, 106, 7400–7404.

  8. Egawa, T., Watanabe, H., Fujimura, T., Ishida, Y., Yamato, M., Masui, D., Shimada, T., Tachibana, H., Yoshida, H., Inoue, H., & Takagi, S. (2011). Novel methodology to control the adsorption structure of cationic porphyrins on the clay surface using the “size-matching rule”. Langmuir, 27, 10722–10729.

  9. Inoue, H., Ichiroku, N., Torimoto, T., Sakata, T., Mori, H., & Yoneyama, H. (1994). Photoinduced electron transfer from zinc sulfide microcrystals modified with various alkanethiols to methyl viologen. Langmuir, 10, 4517–4522.

  10. Ishida, Y., Masui, D., Shimada, T., Tachibana, H., Inoue, H., & Takagi, S. (2012a). The mechanism of the porphyrin spectral shift on inorganic nanosheets: The molecular flattening induced by the strong host–guest interaction due to the “size-matching rule”. The Journal of Physical Chemistry C, 116, 7879–7885.

  11. Ishida, Y., Shimada, T., Tachibana, H., Inoue, H., & Takagi, S. (2012b). Regulation of the collisional self-quenching of fluorescence in clay/porphyrin complex by strong host-guest interaction. The Journal of Physical Chemistry A, 116, 12065–12072.

  12. Ishida, Y., Shimada, T., & Takagi, S. (2014). “Surface-fixation induced emission” of porphyrazine dye by a complexation with inorganic nanosheets. The Journal of Physical Chemistry C, 118, 20466–20471.

  13. Kakegawa, N., Kondo, T., & Ogawa, M. (2003). Variation of electron-donating ability of smectites as probed by photoreduction of methyl viologen. Langmuir, 19, 3578–3582.

  14. Kawamata, J., Suzuki, Y., & Tenma, Y. (2010). Fabrication of clay mineral–dye composites as nonlinear optical materials. Philosophical Magazine, 90, 2519–2527.

  15. Kodaka, M., & Kubota, Y. (1999). Effect of structures of bipyridinium salts on redox potential and its application to CO2 fixation. Journal of the Chemical Society, Perkin Transactions, 2, 891–894.

  16. Kuykendall, V. G., & Thomas, J. K. (1990). Photophysical investigation of the degree of dispersion of aqueous colloidal clay. Langmuir, 6, 1350–1356.

  17. Mao, Y., Breen, N. E., & Thomas, J. K. (1995). Formation of methylviologen radical monopositive cations and ensuing reactions with polychloroalkanes on silica gel surfaces. The Journal of Physical Chemistry, 99, 9909–9917.

  18. Matheson, M. S., Lee, P. C., Meisel, D., & Pelizzetti, E. (1983). Kinetics of hydrogen production from methyl viologen radicals on colloidal platinum. The Journal of Physical Chemistry, 87, 394–399.

  19. Miyata, H., Sugahara, Y., Kuroda, K., & Kato, C. (1987). Synthesis of montmorillonite–viologen intercalation compounds and their photo-chromic behaviour. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 83, 1851.

  20. Miyata, H., Sugahara, Y., Kuroda, K., & Kato, C. (1988). Synthesis of a viologen–tetratitanate intercalation compound and its photochemical behaviour. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 84, 2677.

  21. Ohtani, Y., Ishida, Y., Ando, Y., Tachibana, H., Shimada, T., & Takagi, S. (2014). Adsorption and photochemical behaviors of the novel cationic xanthene derivative on the clay surface. Tetrahedron Letters, 55, 1024–1027.

  22. Palenzuela, J., Vinuales, A., Odriozola, I., Cabanero, G., Grande, H. J., & Ruiz, V. (2014). Flexible viologen electrochromic devices with low operational voltages using reduced graphene oxide electrodes. ACS Applied Materials & Interfaces, 6, 14562–14567.

  23. Peon, J., Tan, X., Hoerner, J. D., Xia, C., Luk, Y. F., & Kohler, B. (2001). Excited state dynamics of methyl viologen. Ultrafast photo-reduction in methanol and fluorescence in acetonitrile. The Journal of Physical Chemistry A, 105, 5768–5777.

  24. Porter 3rd, W. W., & Vaid, T. P. (2005). Isolation and characterization of phenyl viologen as a radical cation and neutral molecule. The Journal of Organic Chemistry, 70, 5028–5035.

  25. Raupach, M., Emerson, W. W., & Slade, P. G. (1979). The arrangement of paraquat bound by vermiculite and montmorillonite. Journal of Colloid and Interface Science, 69, 398–408.

  26. Rytwo, G., Nir, S., & Margulies, L. (1996). Adsorption and interactions of diquat and paraquat with montmorillonite. Soil Science Society of America Journal, 60, 601.

  27. Shichi, T., & Takagi, K. (2000). Clay minerals as photochemical reaction fields. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 1, 113–130.

  28. Solar, S., Solar, W., Getoff, N., Holcman, J., & Sehested, K. (1982). Pulse radiolysis of methyl viologen in aqueous solutions. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 78, 2467.

  29. Sprick, R. S., Bonillo, B., Clowes, R., Guiglion, P., Brownbill, N. J., Slater, B. J., Blanc, F., Zwijnenburg, M. A., Adams, D. J., & Cooper, A. I. (2016). Visible-light-driven hydrogen evolution using planarized conjugated polymer photocatalysts. Angewandte Chemie International Edition, 55, 1792–1796.

  30. Stevenson, M. J., Marguet, S. C., Schneider, C. R., & Shafaat, H. S. (2017). Light-driven hydrogen evolution by nickel-substituted rubredoxin. ChemSusChem, 10, 1–7.

  31. Suquet, H., Iiyama, J. T., Kodama, H., & Pezerat, H. (1977). Synthesis and swelling properties of saponites with increasing layer charge. Clays and Clay Minerals, 25, 231–242.

  32. Suzuki, Y., Tenma, Y., Nishioka, Y., Kamada, K., Ohta, K., & Kawamata, J. (2011). Efficient two-photon absorption materials consisting of cationic dyes and clay minerals. The Journal of Physical Chemistry C, 115, 20653–20661.

  33. Takagi, S., Tryk, D. A., & Inoue, H. (2002). Photochemical energy transfer of cationic porphyrin complexes on clay surface. Journal of Physical Chemistry B, 106, 5455–5460.

  34. Takagi, S., Eguchi, M., Yui, T., & Inoue, H. (2004). Photochemical electron transfer reactions in clay-porphyrin complexes. Clay Science, 12, 82–87.

  35. Takagi, S., Shimada, T., Masui, D., Tachibana, H., Ishida, Y., Tryk, D. A., & Inoue, H. (2010). Unique solvatochromism of a membrane composed of a cationic porphyrin-clay complex. Langmuir, 26, 4639–4641.

  36. Takagi, S., Shimada, T., Ishida, Y., Fujimura, T., Masui, D., Tachibana, H., Eguchi, M., & Inoue, H. (2013). Size-matching effect on inorganic nanosheets: Control of distance, alignment, and orientation of molecular adsorption as a bottom-up methodology for nanomaterials. Langmuir, 29, 2108–2119.

  37. Tokieda, D., Tsukamoto, T., Ishida, Y., Ichihara, H., Shimada, T., & Takagi, S. (2017). Unique fluorescence behavior of dyes on the clay minerals surface: Surface fixation induced emission (s-fie). Journal of Photochemistry and Photobiology A: Chemistry, 339, 67–79.

  38. Toshima, N., Kuriyama, M., Yamada, Y., & Hirai, H. (1981). Colloidal platinum catalyst for light-induced hydrogen evolution from water. A particle size effect. Chemistry Letters, 10, 793–796.

  39. Villemure, G., Detellier, C., & Szabo, A. G. (1986). Fluorescence of clay-intercalated methylviologen. Journal of the American Chemical Society, 108, 4658–4659.

  40. Villemure, G., Detellier, C., & Szabo, A. G. (1991). Fluorescence of methylviologen intercalated into montmorillonite and hectorite aqueous suspensions. Langmuir, 7, 1215–1221.

  41. Wang, Q., Hisatomi, T., Suzuki, Y., Pan, Z., Seo, J., Katayama, M., Minegishi, T., Nishiyama, H., Takata, T., Seki, K., Kudo, A., Yamada, T., & Domen, K. (2017). Particulate photocatalyst sheets based on carbon conductor layer for efficient z-scheme pure-water splitting at ambient pressure. Journal of the American Chemical Society, 139, 1675–1683.

  42. Wasielewski, M. R. (1992). Photoinduced electron transfer in supramolecular systems for artificial photosynthesis. Chemical Reviews, 92, 435–461.

  43. Watanabe, T., & Honda, K. (1982). Measurement of the extinction coefficient of the methyl viologen cation radical and the efficiency of its formation by semiconductor photocatalysis. The Journal of Physical Chemistry, 86, 2617–2619.

  44. Yonemoto, E. H., Riley, R. L., Kim, Y. I., Atherton, S. J., Schmehl, R. H., & Mallouk, T. E. (1992). Photoinduced electron transfer in covalently linked ruthenium tris(bipyridyl)-viologen molecules: Observation of back electron transfer in the Marcus inverted region. Journal of the American Chemical Society, 114, 8081–8087.

Download references

Acknowledgments

This work was partly supported by the PRESTO/JST Program, Innovative Use of Light and Materials/Life; a Grant-in-Aid for Scientific Research on Innovative Areas; a Grant-in-Aid for Scientific Research (B) (No. 24350100); and a Grant-in-Aid for Scientific Research on Innovative Areas “All Nippon Artificial Photosynthesis Project for Living Earth” (AnApple, No. 25107521).

Author information

Correspondence to Takuya Fujimura or Shinsuke Takagi.

Additional information

(Received 15 September 2018; revised 11 December 2019; AE: J. Brendlé-Miehé)

Electronic supplementary material

UV-Vis. absorption spectra of MV2+ aqueous solution, MV2+/SSA complex dispersed in water and MV2+/SSA hybrid film, cartoon of the co-planarization of MV2+ by adsorption on SSA surface, fluorescence spectra of MV2+/SSA hybrid film, UV-Vis absorption spectra of MV2+/SSA hybrid film (0.13% CEC) during UV irradiation (0 to 60 min).

This material is deposited with the Editor-in-Chief and available via the Internet at https://www.clays.org/Journal/JournalDeposits.html

ESM 1

(DOCX 1405 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Fujimura, T., Shimada, T., Sasai, R. et al. Photoreduction of Methylviologen in Saponite Clay: Effect of Methylviologen Adsorption Density on the Reaction Efficiency. Clays Clay Miner. (2020). https://doi.org/10.1007/s42860-019-00047-8

Download citation

Keywords

  • Methylviologen
  • Organic molecule−clay complex
  • Photoinduced electron transfer
  • Photoreduction
  • Self-fluorescence quenching hybrid film
  • Smectite