分光電気化学測定法の紹介 - bas.co.jp

1 15 1. (Spectroelectrochemistry, SEC) 1) 2 , 3) , 4) 6) SEC 7) 9) 10 , 11) SEC / 12) 2. 13) 14 , 15) in situ (Thin Layer Fig.

2 1 Principle of TLC when using transparent and minigrid electrodes. (50 ~ 200 m) 16 Cell, TLC) OTE(optically transparent electrode) (grid electrode) 3. ( ) ALS2323 SEC2000 ALS2323 1 2 7 16 bit D/A 16 bit A/D ALS2323 SEC2000 Fig. 2 ALS2323 Electrochemical analyzer withSEC2000.

3 Fig. 3 ALS2323 Electrochemical analyzer. Fig. 4 Schematic diagram of SEC2000 Spectroelectrochemical system with SEC-C. 17 SEC-C SEC-C 1mm (Wo r k i n g E l e c t r o d e , WE) (Au Pt ) (Reference Electrode, RE) Ag Ag/AgCl (Counter Electrode, CE) SEC-C 2mM Fe (CN)63- / Fe (CN)64- KNO3 CV V Fe (CN)63-/ Fe (CN)64- 300 nm 420 nm V V 250 nm 280 nm 350 nm 460 nm ( ) ( ) Fe(CN)63- + e- Fe(CN)64- (Red time) (1) Fe(CN)64- Fe(CN)63- + e- (Ox time)

4 (2) Fig. 5 SEC-C Thin Layer Quartz GlassSpectroelectrochemical cell kit. Fig. 6. Cyclic voltammogram of 2mM K3[Fe(CN)6]. 18 Fig. 7. Absorbance measurement of 2 mM K3[Fe(CN)6]. SEC-F (Spectroelectrochemistry-Flow Cell, SEC-F ) SEC-F in siut SEC-F ITO (Indium-Tin-Oxide) Au, Pt ITO 350nm Au, Pt Fig. 8 Schematic diagram of SEC-F. Light SourceInletOutleInlet OutletFlow cell block1. Collimating Lens 2. SEC-FT500 Teflon gasket 3. Working electrode 4. Reference electrode 5. Probetype Optical fiber (Counter Electrode) 6. Flow cell block (A) 7. Flow cell Block (B) 8.

5 Dynaseal PEEK 19 4. CV E0 , n 16 , 17) 18) 19) Fig. 10 The transmittance of ITO electrode and quartz. Comparison of the transmittance mm, 1 mm quartz glass substrate with /without ITO film on. SEC2000-UV/VIS Spectrometer Optical Fiber Electrochemical Analyzer Spectroelectrochemical flow cell Light Source Fig. 9 Schematic diagram of SEC-F with spectroelectrochemical measurement system. 20 4. 1. Ru [Ru bipy 3]2+ UV 104 M-1cm-1 20) ALS2323 CV V SEC-C V V 450 nm 280 nm 310 nm 450nm MLCT metal to ligand charge transfer 450nm Ru II Ru III 280nm Ru II Ru III bpy 450nm Ru 280 330 380 430 480 530 580 630wavelength [nm]ODb Fig.

6 12 Changes of spectrum when [Ru bipy 3]2+ is electrically oxidized at V(a) and V (b). a CV measurement of 3,3'-dimethylbenzidine 21 Ru II bpy Ru(III) V Ru Cl- 1 mM Ru bipy 3Cl2 Bard 21) CV Ru V V Cl- 5. 5,6) - / IIII 22++ IIIIII 33++ 22++**ee--ee ++ee Fig. 13 Cyclic voltammogram of 1 mM Ru(bipy)sCl2 in acetonitrile at a Pt electrode with M TBABF, supporting rate = 100 mV/sec scan from to + V.

7 The dotted portion marks the 10-methyl-phenothia-zine oxidation wave. 22 1 R. J. Gale Ed., Spectroelectrochemistry: Theory and Practice, Plenum Press, New York (1988) 2 D. M. Kolb; Spectroelectrochemistry (Edited by R. J Gale), p 87 (Plenum Press, 1988) 3 W. Plieth; Spectroscopic and Diffractioin Techniques in Interfacial Electrochemistry (Edited by C. Gutierrez and C. Melendres), p. 223 (Kluwer Academic Publishers, 1990) 4 , , 42, 127 (1993). 5 T. Sagara, M. Fukuda and N. Nakashima, J. Phys. Chem., B, 102, 521 (1998). 6 T. Sagara, N. Kaba, M. Komatsu, M. Uchida and N. Nakashima, Electrochim. Acta, in press. 7 P. Zanello, Inorganic electrochemistry , The Royal Society of Chemistry, (2003) 8 A. J. Bard and L. R. Faulkner, Electrochemical Methods , 2nd Ed., Wiley, New York (2001). 9 Dhawan, I. K., Shelver, D., Thorsteinsson, M.

8 V., Roberts, G. P., and Johnson, M. K. (1999) biochemistry 39, 12805-12813 10. T. P. DeAngelis and W. R. Heineman, J. Chem. Ed ., 53m 594 (1976). 11. D. E. Aspnes, N. Bottka: Semiconductors and Semimetals , Edited by R. K. Willardson, C. A. Speer, Vol. 9 (1972), (Academic Press, New York). 12. W. R. Heineman, Anal. Chem. , 50, 390a (1978). 13. C. H. Su, W. R. Heineman. Anal. Chem., 53, 594 (1983). 14. (1973). 15 14 (1984). 16. M. Haga, M. M. Ali, H. Maegawa, K, Nozaki, A. Yoshimura, T. Ohno, Rev., 132,99 (1994) 17 Wei Zhou, Shen Ye, Masaaki Abe, Takuma Nishida, Kohei Uosaki, Masatoshi Osawa, and Yoichi Sasaki, Chem. Eur. J.,Vol. 11, No. 17, pp. 5040-5054, 18. A. J. Bard and L. R. Faulkner, "Electrochemical Methods", Wiley, New York , 1980, chap. 14. 19. Hiroshi , N., Yumiko, H.

9 , Toshifumi T., The Journal of Biological Chemistry, Vol. 276m Bi, 10, Issue of March 9, pp. 7055-7061, 2001. 20. > > > 21. Nurhan E. Tokel, Allen J. Bard, Journal of the American Chemical Society 94:8 April 19, 1972