Surface-enhanced IR absorption spectroscopy

LC-IR using surface-enhanced IR absorption spectroscopy (SEIRAS) was recently designed in order to develop a highly sensitive and rapid analysis method for polymer additives [506]. The method, which consists of spraying the LC eluents on to a metal film of Ag on a BaF2 substrate, allows an enhancement factor of about 90. 

A new in situ Fourier transform IR (Fl lR) method, surface-enhanced IR absorption spectroscopy (SEIRAS Osawa 1997), was employed that could observe the surface of the platinum electrode on a silicon prism while electrochemically polarizing it in... 

Fig. 7 Surface-enhanced IR absorption spectroscopy spectra of platinum on silicon in 0.1 mol dm" HCIO at various potentials under N. (dotted line), in 0.1 mol dm" CH5OH + Ommol dm" bpy (dashed line), in Omol dm" CH OH + 0.1 mmol dm" bpy (line), in 0.1 mol dm" CH3OH + 0.1 mmol dm" bpy. Left OH stretching band, right HOH bending band, formate and perchlorate bands. (Reproduced from Shiroishi et al. 2003, copyright the American Chemical Society)...

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. 

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. 

Enhancement of absorption bands in the IR spectra of ultrathin films in the presence of discontinnons (islandlike) nnder- and ovemanolayers of Ag and An was discovered by Hartstein et al. [356] in the early 1980s. Although these researchers believed that they observed an increase in the vCH band intensities for p-nitro-benzoic acid (p-NBA), benzoic acid, and 4-pyridine-COOH films, it was recently shown [350] that the spectra reported are in actual fact due to fully saturated hydrocarbons (possibly vacuum pump oil). In any case, this discovery has stimulated various research activities and led to the development of surface-enhanced IR absorption (SEIRA) spectroscopy. To date, the SEIRA phenomenon has been exploited in chemical [357] and biochemical IR sensors (see [357-360] and literature therein), in studying electrode-electrolyte interfaces [171, 361-365], and in LB films and SAMs [364, 366-370]. Other metals that demonstrate this effect are In [371] and Cu, Pd, Sn, and Pt [372-375]. The metal films can be prepared by conventional metal deposition procedures such as condensation of small amounts of metal vapor on the substrate, spin coating of a colloidal solution, electrochemical [388], or reactive deposition [299] (see also Section 4.10.2). 

Figure 14 Surface-enhanced time-resolved IR reflection spectra monitoring the adsorption and desorption of fumaric acid on a gold electrode. (Reproduced with permission from Osawa M (2002) Surface-enhanced infrared absorption spectroscopy. In Chalmers JM and Griffiths PR (eds.) Handbook of Vibrational Spectroscopy, vol. 2, pp. 785-799. Chichester Wiley John Wiley Sons Ltd.)...

Itmumerable mechanistic studies of alcohol oxidation on Pt-based electrocatalysts in acidic media have been published over the last few years. Methanol, " ethanol ° and ethylene glycol have been the most studied substrates and their oxidation paths on Pt or Pt alloys have been substantiated using a variety of in situ, extra situ and operando techniques as well as quantum mechanical calculations. The experimental techniques include reflection IR spectroscopy (IR), surface enhanced IR asbsorption spectroscopy (SEIRAS), " attemrated total reflection-IR absorption spectroscopy (ATR-IRAS), differential electrochemical mass spectroscopy (DEMS), single potential alteration IR spectroscopy... 

Other methods for studying nucleic acids and their complexes include infrared spectroscopy. By use of surface-enhanced infrared absorption spectroscopy, in situ hybridisation kinetics have been measured,and detection of formation of G-quadruplexes has been studied using a combination of IR and vibrational circular dichroism. ° ... 

Sun SG, Cai WB, Wan LJ, Osawa M. 1999. Infrared absorption enhancement for CO adsorbed on Au films in perchloric acid solutions and effects of surface structure studied by cyclic voltammetry, scanning tunneling microscopy, and surface-enhanced IR spectroscopy. J Phys Chem B 103 2460-2466. 

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. 

Cation radicals of several metallated TPP and OEP complexes were reported to have unique IR active ring modes (21. These absorptions were observed in the region 1250-1290 cm for TPP complexes and 1520-1570 cm for OEP complexes. IR and raman active modes have also been observed for several different reduced oxygen species adsorbed on various metal substrates. Observations of the adsorption of oxygen on silver by surface enhanced raman spectroscopy (SERS) 22), show superoxide molecules (O2) have a frequency of 1053 cm, and peroxide (0 ) of 697 cm. This same study reported additional peaks were observed at 815 cm and 1286... 

The mechanism of C02 reduction to methane at Cu electrodes has been proposed by various groups [72-74], most of which involved the splitting of adsorbed CO followed by the hydrogenation of surface C atoms. When DeWulf et al. used X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy to study the reaction [72], they observed surface-bound carbenes (Cu CH2) as an intermediate in the system. Likewise, others used both in situ infrared (IR) reflection absorption spectroscopy and surface-enhanced Raman spectroscopy to observe the initial product of C02 reduction on Cu [74]. Typically, two different linearly bound CO species were identified and attributed to adsorption on either surface defect sites or terraces. 

With infrared reflection absorption spectroscopy (IRRAS), it is possible to obtain information about the orientation of enzyme molecules adsorbed on flat metal surfaces (3,4). Electric dipole-transition moments oriented perpendicular to a flat metal surface show enhanced IR absorbance. IR bands due to vibrations of groups with transition moments oriented parallel to the surface are not observed. The IR-beam component which is polarized perpendicular to the plane of incidence (parallel to the surface) contains no information and can be eliminated by using a polarizer. 

Palladium nanoparticles (nm-Pd) were synthesized by ship-in-a-bottle technique in supercages of NaA zeolite. The behaviors of electrodes of thin film of nm-Pd accommodated in NaA zeolite were characterized by cyclic voltammetry. The results illustrated that the nm-Pd possess particular properties for hydrogen reaction, i.e. in contrast to hydrogen absorption on massive palladium electrode, the surface processes of hydrogen adsorption-desorption become the dominant reaction on electrodes of thin film of nm-Pd. The processes of adsorption and desorption of carbon monoxide on the electrodes were studied using in situ electrochemical FTIR reflection spectroscopy. It has been revealed that in comparison with CO adsorbed on a massive Pd electrode, the IR absorption of CO adsorbed on nm-Pd particles accommodated in NaA zeolite has been enhanced to about 36 times. 

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