Subtractively Normalized Interfacial Fourier Transform Infrared Spectroscopy

Figure 6.18 Subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS) spectra of a polished polyciystaUine Pt electrode, immersed in 0.1 M HCIO4, + 5 M CH3OH electrolyte. All spectra were normahzed to the base spectrum collected at 0 mV vs. RHE. (Reproduced from Iwasita and Vielstich [1988].)...

Subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS), has been used extensively to examine interactions of species at the electrode/electrolyte interface. In the present work, the method has been extended to probe interactions at the mercury solution interface. The diminished potential dependent frequency shifts of species adsorbed at mercury electrodes are compared with shifts observed for similar species adsorbed at d-band metals. 

Subtractively normalized interfacial Fourier transform infrared spectroscopy has been used to follow the reorientations of isoquinoline molecules adsorbed at a mercury electrode. Field induced infrared absorption is a major contribution to the intensities of the vibrational band structure of aromatic organic molecules adsorbed on mercury. Adsorbed isoquinoline was observed to go through an abrupt reorientation at potentials more negative than about -0.73 V vs SCE (the actual transition potential being dependent on the bulk solution concentration) to the vertical 6,7 position. 

The SNIFTIRS approach. The acronym SNIFTIRS means Subtractively Normalized Interfacial Fourier Transform Infrared Spectroscopy. The basic concept of this method involves the fact that the raw data obtained directly from the Fourier Transform process contain components which are undesirable. Firstly, there is material in the solution which may have affected the spectrum. Secondly, unwanted information on certain material on the electrode (adsorbed water, for example) is best eliminated. 

Hamelin [47] has shown that specific adsorption of OH ions increases in the following order Au(lll) < Au(lOO) < Au(311). Chen and Lipkowski [48] have applied chronocoulometry and subtractively normalized interfacial Fourier transform infrared spectroscopy to study adsorption of hydroxide ions on Au(lll) electrode. This process proceeded in three steps. Bonding of OH with gold atoms that is quite polar at negatively charged surface becomes less polar at positively... 

Subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTRS). Using an FTIR spectrometer, multifrequency... 

CO adsorption on Cu electrode surface is interfered with by specifically adsorbed anions. CO can be adsorbed below a certain definite potential, determined by the adsorption strength of CO and the anion. When CO molecules displace the specifically adsorbed anions on Cu electrode, a voltammetric peak is observed as exemplified for Cu(lOO) in CO saturated phosphate buffer solution in comparison with N2 saturated solution (Fig. 29). Subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS) spectra in Fig. 30 demonstrates that CO is adsorbed at -0.8 V vs. SHE but not at -0.4 V, and adsorbed phosphate anion vice versa. " This process is equivalent to charge displacement adsorption of CO on Pt electrode revealed by Clavilier et al The profile of the voltammogram depends greatly on the crystal... 

Pons [133] reported a slightly more sophisticated data acquisition protocol, which he termed SNIFTIRS (subtractively normalized interfacial Fourier transform infrared spectroscopy), which involved stepping the potential of the reflective working electrode repeatedly between two preset values, as shown in Fig. 11(d). The... 

SNIFTIRS subtractively normalized interfacial Fourier transform infrared spectroscopy... 

Surface-extended X-ray absorption fine structure (analysis) spectroscopy Sum frequency generation Second harmonic generation Surface ionization Secondary ion mass spectroscopy Subtractively normalized interfacial Fourier transform infrared spectroscopy Single potential alteration infrared (spectroscopy)... 

As it was shown by SNIFTIRS measurements (subtractively normalized interfacial Fourier transform infrared spectroscopy measurements) that adsorbed CO species exist from 0.3 V vs RHE on a Pt surface ... 

Table 17.15 shows results obtained from the application of various bulk and surface analysis methods to lithium metal at rest or after cyclization experiments, as well as at noble metal and carbon electrodes after cathodic polarization. Several surface and elemental analysis methods are applied, including X-ray photoelectron spectroscopy (XPS, ESCA/XPS), energy dispersive analysis of X-rays (X-ray microanalysis, EDAX), Eourier transform infrared spectroscopy (ETIR), Auger electron spectroscopy (AES), ellipsometry (E), electro-modulated infrared reflectance spectroscopy (EMIRS), double modulation Fourier transform infrared spectroscopy (DMFTIR), subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS), gas chromatography (GC), IR spectroscopy. X-ray diffraction (XRD), and atomic force microscopy (AFM). 

The decomposition of chloro-EC on a graphite electrode (formation of SEI) was investigated using two in situ techniques subtractively normalized interfacial Fourier transform infrared spectroscopy (SNlF ilKS) and differential electrochemical mass spectrometry (OEMS) [45]. The applied analytical methods provided conforming information about the onset of CO2 formation (2.2-2.1 Vvs. U/Li ). Hydrogen is evolved below ca 0.6 VLi/Li. ... 

Subtractively Normalized Interfacial Fourier Transform Infrared Spectroscopy (SNIFTIRS). Pons et have developed the SNIFTIRS technique,... 

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