Fourie Transform Infrared Spectroscopic Studies on Organic Electrode Reactions

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FTIF spectroelectrochemistry of various electrode/solution interfaces has been examined in this research project. Followings are main achievements.1. A measuring assembly has been set up for interfacial FTIR spectroelectrochemistry. Use of high sensitive detector, such as MCT detector, and preparation of suitable spectroelectrochemical cell are very important to obtain well defined signals.2. Redox reactions of some cyanometal complexes have been examined using the prepared set up: Oxidation processes of cyanide and ferrocyanide ions were monitored by the C-N stretching vibration at Pt and Au electrodes; CNO<@D1-@>D1 and ferricyanide ions were detected, respectively. For octacyano tungstate(IV) and molybdate(IV), the wave number for the C-N stretching vibration was almost independent of the oxidation state of the central metal. At a gold electrode cyanocomplexes showed rather complicated signals because of dissociation of the electrode. W(CN)<@D34-(/)8@>D3 adsirbed more strongly than CN<@D1-@>D1 onto a gold electrode. No AuCN formation was observed during oxidation of W(CN)<@D24-(/)8@>D3 while AuCN was formed at the electrode surface at high positive potentials during oxidation of Mo(CN)<@D34-(/)8@>D3. Au(CN)<@D3-(/)2@>D3 oxidized at a Pt electrode to give AuCN and CNO<@D1-@>D1 in the absence of excess amounts of CN<@D1-@>D1 or halides;Au(CN)_2 +H_2 - 2e AuCN + CNO^- + 2H^+.3. Thin films of some organic compounds, such as methylviologen, cytochrome c, electropolymerized organic thin films and so on, at the electrode surface were monitored as a function of electrode potential. However, further improvements of the measuring system have been required to get signals due to species adsorbed on the electrode by monolayer; use of modulation techniques would be helpful.