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

Published online by Cambridge University Press:  01 January 2024

Takuya Fujimura ,
Tetsuya Shimada ,
Ryo Sasai  and
Shinsuke Takagi
Takuya Fujimura*
Affiliation:
Department of Materials Chemistry, Graduate School of Natural Science & Technology, Shimane University, 1060, Nishikawatsu-cho, Matsue, Shimane 690-8504, Japan
Tetsuya Shimada
Affiliation:
Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo 192-0397, Japan Center for Artificial Photosynthesis, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo 192-0397, Japan
Ryo Sasai
Affiliation:
Department of Materials Chemistry, Graduate School of Natural Science & Technology, Shimane University, 1060, Nishikawatsu-cho, Matsue, Shimane 690-8504, Japan
Shinsuke Takagi*
Affiliation:
Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo 192-0397, Japan Center for Artificial Photosynthesis, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo 192-0397, Japan
*
*E-mail address of corresponding author: tfujimura@riko.shimane-u.ac.jp
*E-mail address of corresponding author: takagi-shinsuke@tmu.ac.jp
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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.

Keywords

MethylviologenOrganic molecule−clay complexPhotoinduced electron transferPhotoreductionSelf-fluorescence quenching hybrid filmSmectite
Type
Article
Information
Clays and Clay Minerals , Volume 67 , Issue 6 , December 2019 , pp. 537 - 544
Copyright
Copyright © Clay Minerals Society 2019

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