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.
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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).
(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).
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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
- Organic molecule−clay complex
- Photoinduced electron transfer
- Self-fluorescence quenching hybrid film