Surfaced enhanced infrared absorption

Osawa, M Tsushima, M Mogami, H., Samjeske, G. and Yamakata, A. (2008) Structure of water at the electrified platinum-water interface a study by surface-enhanced infrared absorption spectroscopy. J. Phys. Chem. C, 112, 4248- 256. 

Yamakata, A., Uchida, T., Kubota, J. and Osawa, M. (2006) Laser-induced potential jump at the electrochemical interface probed by picosecond time-resolved surface-enhanced infrared absorption spectroscopy./. Phys. Chem. B, 110, 6423-6427. 

Samjeske G, Miki A, Ye S, Osawa M. 2006. Mechanistic study of electrocatal3dic oxidation of formic acid at platinum in acidic solution by time-resolved surface-enhanced infrared absorption spectroscopy. J Phys Chem B 110 16559-16566. 

A related effect has been described for IR spectroscopy - Surface Enhanced Infrared Absorption spectroscopy (SEIRA). However, as the enhancement factors are significantly lower than for SERS and both the required metal particle size and the activation distance between the target molecule and the particle are more than one order of magnitude smaller, no practically applicable SEIRA sensors have been demonstrated up to now. 

Osawa, M., Surface enhanced infrared absorption, In Near Field Optics and Plasmon Polar itons Kawata, S., Ed. Springer, Berlin, 2001, 163 187... 

The mechanism of dissolution of the Cu UPD layer on Au(lll) has been studied by Ataka etal. [409]. The monolayer comprised Cu in 2/3 and sulfate in 1/3 proportions. It has been found by applying time-resolved surface-enhanced infrared absorption spectroscopy and chronoam-perometry that dissolution proceeds in two steps. In the first step, 1/3 Cu monolayer and all sulfate anions are removed via the Langmuir-type kinetics. In the second step, the rest of Cu is desorbed via nucleation and growth kinetics. 

Alternatively, various analytical methods based on SPR phenomenon have been developed, including surface plasmon field-enhanced Raman scattering (SERS) [7], surface plasmon field-enhanced fluorescence spectroscopy (SPFS) [8-11], surface enhanced second harmonic generation (SHG) [12], surface enhanced infrared absorption (SEIRA) [13], surface plasmon field-enhanced diffraction spectroscopy (SPDS) [14-18], Most of these methods take advantage of the greatly enhanced electromagnetic field of surface plasmon waves, in order to excite a chromophoric molecule, e.g., a Raman molecule or a fluorescent dye. Therefore, a better sensitivity is expected. 

Fig. 1. (a) A chemical structure of a 2.5th generation carboxylic acid-terminated poly(amido amine) (PAMAM) dendrimer. (b) Transmission surface enhanced infrared absorption spectra (SEIRAS) of dendrimer adlayers prepared at 30 min adsorption from aqueous solutions (0.01 wt.%) of a dendrimer at different pHs. Numerical values are pHs of the solutions, (c) Adsorption-desorption profiles as a function of time at different pHs and adlayer thicknesses at adsorption and desorption equilibrium as a function of pH for aqueous solutions (0.1 wt.%) of the dendrimer. The symbols, j and J, in the top figure denote start of adsorption and desorption, respectively. In the bottom figure, filled circle and opened square denote adlayer thicknesses at adsorption and desorption equilibrium, respectively. The dark tie denotes the calculated dendrimer size width. A solid curve is drawn to be visual, (d) Schematic illustration of dendrimers adsorbed at different pHs. Reprinted with permission from Ref. [69], 2006, American Scientific Publishers. 

Furthermore, it is possible to increase the sensitivity of the IR technique, and thus the probability of detecting transient surface species characterized by (very) low absorption coefficients (such as the intermediate species present during the first steps of the polymerization reaction on the Phillips catalyst) by exploiting the surface-enhanced infrared absorption (SEIRA) effect. It is known that molecules adsorbed on metal island films or particles exhibit 10-1000 times more intense infrared absorption than would be expected from conventional measurements without the metal (253-256). The possibility of performing SEIRA spectroscopy should therefore be expected to provide an opportunity to better investigate the nature of the intermediate species, not only for ethene polymerization on Cr(II)/ Si02, but for other reactions on solid catalysts. 

SIERA Surface-enhanced infrared absorption As in the case of surface-enhanced Raman scattering (SERS), molecules adsorbed on metal island films or particles exhibit intense infrared absorption several folds higher than what one would expect from conventional measurements without the metal. This effect is referred to as surface-enhanced infrared absorption (SEIRA). 

Sudo, E. Esaki, Y. Sugiura, M. Analysis of additives in a polymer by LC/IR using surface-enhanced infrared absorption spectroscopy. Bunseki Kagaku 2001, 50, 703-707. 

Since the enhancement of IR absorption is one of the important characteristics in abnormal IR effects, it may be interesting to compare the AIREs with the phenomenon of surface-enhanced infrared absorption (SEIRA) reported in the literature. The SEIRA was discovered by Hartstein et al. [96] in the early 1980s and describes the phenomenon of the enhancement of IR absorption for some specific... 

Surface enhanced infrared absorption (SEIRA) has been observed in external reflection spectroscopy [185], for further details, see Sect. 5.2.5. 

Surface Enhanced Infrared Absorption Spectroscopy (SEIRAS)... 

Instrumentation. In order to employ local enhancement of infrared absorption by surface plasmon polaritons that cause locally enhanced surface electromagnetic fields, a suitable optical arrangement is needed [295]. Surface enhanced infrared absorption spectroscopy can also be observed in the transmission mode [285, 296]. However, since no application of this approach in spectroelectrochemistry has been reported so far, it is not discussed further. 

SEIRAS Surface enhanced infrared absorption spectroscopy... 

These ions undergo only weak perturbations upon adsorption. Thus, it can be difficult to discriminate species in solution, or in the diffuse doublelayer, from ions at the electrode surface [54]. Better selectivity for adsorbed electrolyte anions has been achieved through use of the surface-enhanced infrared absorption spectroscopy (SEIRAS) technique [22, 54, 89, 90]. Methods for the preparation of quasi-single crystalline thin films are enabling the study of electrolyte adsorption on structurally well-defined surface sites by SEIRAS [22, 89,... 

The phenomenon of surface-enhanced infrared absorption (SEIRA) spectroscopy involves the intensity enhancement of vibrational bands of adsorbates that usually bond through contain carboxylic acid or thiol groups onto thin nanoparticulate metallic films that have been deposited on an appropriate substrate. SEIRA spectra obey the surface selection rule in the same way as reflection-absorption spectra of thin films on smooth metal substrates. When the metal nanoparticles become in close contact, i.e., start to exceed the percolation limit, the bands in the adsorbate spectra start to assume a dispersive shape. Unlike surface-enhanced Raman scattering, which is usually only observed with silver, gold and, albeit less frequently, copper, SEIRA is observed with most metals, including platinum and even zinc. The mechanism of SEIRA is still being discussed but the enhancement and shape of the bands is best modeled by the Bruggeman representation of effective medium theory with plasmonic mechanism pla dng a relatively minor role. At the end of this report, three applications of SEIRA, namely spectroelectrochemical measurements, the fabrication of sensors, and biochemical applications, are discussed. 

Over recent years, internal reflectance infrared studies have tended to concentrate on the study of relatively thick films of conducting polymers or layers, (see, for example, the work of Pham and coworkers [49, 50], or Kvarn-strom, Nauer, Neugebauer and coworkers [51-54]) in which sensitivity was not a particular problem, or on the semiconductor-electrolyte interface, (see the work of Chazalviel and coworkers [35, 40, 41]), in which the SPP excitation approach is not appropriate. However, interest has focused again on this phenomenon with the surface-enhanced infrared absorption spectroscopy (SEIRAS) studies of Osawa and coworkers [19, 26, 27, 46, 55, 56], who have combined the application of the Kretschmann configuration with step-scan FTIR spectroscopy to study fast, reversible electrochemical processes on timescales down to microseconds [26, 46, 57-60]. 

Miyake H, Okada T, Samjeske G et al (2008) Formic acid electrooxidatirai on Pd in acidic solutions studied by surface enhanced infrared absorption spectroscopy. Phys Chem Chem Phys 10 3662-3669... 

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