title: In operando observation system for electrochemical reaction by soft X-ray absorption spectroscopy with potential modulation method.
abstract: In order to investigate local structures of electrolytes in electrochemical reactions under the same scan rate as a typical value 100 mV/s in cyclic voltammetry (CV), we have developed an in operando observation system for electrochemical reactions by soft X-ray absorption spectroscopy (XAS) with a potential modulation method. XAS spectra of electrolytes are measured by using a transmission-type liquid flow cell with built-in electrodes. The electrode potential is swept with a scan rate of 100 mV/s at a fixed photon energy, and soft X-ray absorption coefficients at different potentials are measured at the same time. By repeating the potential modulation at each fixed photon energy, it is possible to measure XAS of electrochemical reaction at the same scan rate as in CV. We have demonstrated successful measurement of the Fe L-edge XAS spectra of aqueous iron sulfate solutions and of the change in valence of Fe ions at different potentials in the Fe redox reaction. The mechanism of these Fe redox processes is discussed by correlating the XAS results with those at different scan rates.
authors.affiliation: Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan.
authors.forename: Masanari
authors.initials: M
authors.lastname: Nagasaka
authors.affiliation: Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan.
authors.forename: Hayato
authors.initials: H
authors.lastname: Yuzawa
authors.affiliation: Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan.
authors.forename: Toshio
authors.initials: T
authors.lastname: Horigome
authors.affiliation: Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan.
authors.forename: Nobuhiro
authors.initials: N
authors.lastname: Kosugi