Infrared spectroscopy surface acidity

The most powerful tool for the characterization of acidic groups in solid surfaces is infrared spectroscopy. Since this method enables the measurement of the extent of protonation of a chemisorbed base, the chief handicap of the previously described methods has been overcome the amount of basic reagent required to neutralize Br0nsted acids can be distinguished from that attached to a catalyst surface by other types of chemical bonds. Several general reviews are already available that deal with the infrared spectroscopy of solid surfaces (37-39). Our discussions of this tool will therefore be limited to some of the highlights in the application of infrared spectroscopy for the determination of surface acidity. 

Chemical interactions The chemical contribution may result from interactions such as covalent or complex bond formation between the surfactants and the surface sites. Surfactants such as fatty acids, alkyl sulfates, alkyl sulfonates, amines and alkylhydroxa-mates have been proposed to adsorb by means of chemical interactions on a variety of particles. In addition, surfactants containing hydroxyl, phenolic, carboxylic and amine groups can hydrogen-bond with the surface sites. Infrared spectroscopy has been used to understand the chemisorption of surfactants at the surface, by examining the shift in the characteristic peaks of the surfactants upon adsorption. 

Peng et al. combined electrochemical surface-enhanced infrared spectroscopy (EC-SEIRAS) and DFT calculations to probe the Sb adatom enhancement mechanism on polycrystalline Pt surfaces [27]. The forward cyclic voltammogram in 0.1 M formic acid and 0.5 M H2SO4 showed a 2.7 x decrease in COads at potentials below 0.2 V versus RHE for a 0.6 mraiolayer (ML) Sb, with a tenfold current increase at 0.5 V in the forward scan. They concluded at coverages >0.25 ML that the [Sb] [Pt] dipole interacticHi enhances CH-down adsorption. This is consistent with Leiva et al. s work presented above. They additionally attributed this coverage dependence to a decrease in the Pt-COads bond strength with increased Sb coverage. 

Peng B, Wang H-F, Liu Z-P, Cai W-B (2010) Combined surface-enhanced infrared spectroscopy and first-principles study on electro-oxidation of formic acid at Sb-modified Pt electrodes. J Phys Chem C 114 3102-3107... 

Samjeske G, Miki A, Ye S, Osawa M. Mechanistic study of electrocatalytic oxidation of formic acid at platinum in acidic solution by time-resolved surface-enhanced infrared spectroscopy. J Phys Chem B 2006 110 16559-66. 

Still another type of adsorption system is that in which either a proton transfer occurs between the adsorbent site and the adsorbate or a Lewis acid-base type of reaction occurs. An important group of solids having acid sites is that of the various silica-aluminas, widely used as cracking catalysts. The sites center on surface aluminum ions but could be either proton donor (Brpnsted acid) or Lewis acid in type. The type of site can be distinguished by infrared spectroscopy, since an adsorbed base, such as ammonia or pyridine, should be either in the ammonium or pyridinium ion form or in coordinated form. The type of data obtainable is illustrated in Fig. XVIII-20, which shows a portion of the infrared spectrum of pyridine adsorbed on a Mo(IV)-Al203 catalyst. In the presence of some surface water both Lewis and Brpnsted types of adsorbed pyridine are seen, as marked in the figure. Thus the features at 1450 and 1620 cm are attributed to pyridine bound to Lewis acid sites, while those at 1540... 

Several properties of the filler are important to the compounder (279). Properties that are frequentiy reported by fumed sihca manufacturers include the acidity of the filler, nitrogen adsorption, oil absorption, and particle size distribution (280,281). The adsorption techniques provide a measure of the surface area of the filler, whereas oil absorption is an indication of the stmcture of the filler (282). Measurement of the sdanol concentration is critical, and some techniques that are commonly used in the industry to estimate this parameter are the methyl red absorption and methanol wettabihty (273,274,277) tests. Other techniques include various spectroscopies, such as diffuse reflectance infrared spectroscopy (drift), inverse gas chromatography (igc), photoacoustic ir, nmr, Raman, and surface forces apparatus (277,283—290). 

Recent developments in the mechanisms of corrosion inhibition have been discussed in reviews dealing with acid solutions " and neutral solu-tions - . Novel and improved experimental techniques, e.g. surface enhanced Raman spectroscopy , infrared spectroscopy. Auger electron spectroscopyX-ray photoelectron spectroscopyand a.c. impedance analysis have been used to study the adsorption, interaction and reaction of inhibitors at metal surfaces. 

Chang SC, Ho Y, Weaver MJ. 1992. Applications of real-time infrared spectroscopy to electrocatalysis at bimetallic surfaces. I. Electrooxidation of formic acid and methanol on bismuth-modified platinum (111) and platinum (100). Surf Sci 265 81-94. 

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. 

The specific surface area of the fresh and used catalysts was measured by nitrogen adsorption method (Sorptometer 1900, Carlo Erba Instruments). The catalysts were outgassed at 473 K prior to the measurements and the Dubinin equation was used to calculate the specific surface area. The acidity of investigated samples was measured by infrared spectroscopy (ATI Mattson FTIR) by using pyridine (>99.5%, a.r.) as a probe molecule for qualitative and quantitative determination of both Bronstcd and Lewis acid sites (further denoted as BAS and LAS). The amounts of BAS and LAS were calculated from the intensities of corresponding spectral bands by using the molar extinction coefficients reported by Emeis (23). Full details of the acidity measurements are provided elsewhere (22). 

Ir spectra, of surface layers, 24 110. See also Infrared reflection-absorption spectroscopy (IRRAS) ir spectrometers, 23 132 Ir (infrared) spectroscopy, for analysis of MF resins, 15 790. See also Infrared technology Isanic acid, 5 34t... 

Spectroscopic techniques may provide the least ambiguous methods for verification of actual sorption mechanisms. Zeltner et al. (Chapter 8) have applied FTIR (Fourier Transform Infrared) spectroscopy and microcalorimetric titrations in a study of the adsorption of salicylic acid by goethite these techniques provide new information on the structure of organic acid complexes formed at the goethite-water interface. Ambe et al. (Chapter 19) present the results of an emission Mossbauer spectroscopic study of sorbed Co(II) and Sb(V). Although Mossbauer spectroscopy can only be used for a few chemical elements, the technique provides detailed information about the molecular bonding of sorbed species and may be used to differentiate between adsorption and surface precipitation. 

Suitable characterization techniques for surface functional groups are temperature-programmed desorption (TPD), acid/base titration [29], infrared spectroscopy, or X-ray photoemission spectroscopy, whereas structural properties are typically monitored by nitrogen physisorption, electron microscopy, or Raman spectroscopy. The application of these methods in the field of nanocarbon research is reviewed elsewhere [5,32]. 

As Smith (300) has shown by infrared spectroscopy, carboxylic acids are adsorbed either by hydrogen bonding of the carboxyl group or by proton transfer to the surface. Carboxylate absorptions were observed in the spectra. Very likely O " or OH ions acted as proton acceptors although no OH absorption bands could be detected after carboxylic acid adsorption. The isoelectric point of pure anatase is near pH 6.6 (305). 

We then designed model studies by adsorbing cinchonidine from CCU solution onto a polycrystalline platinum disk, and then rinsing the platinum surface with a solvent. The fate of the adsorbed cinchonidine was monitored by reflection-absorption infrared spectroscopy (RAIRS) that probes the adsorbed cinchonidine on the surface. By trying 54 different solvents, we are able to identify two broad trends (Figure 17) [66]. For the first trend, the cinchonidine initially adsorbed at the CCR-Pt interface is not easily removed by the second solvent such as cyclohexane, n-pentane, n-hexane, carbon tetrachloride, carbon disulfide, toluene, benzene, ethyl ether, chlorobenzene, and formamide. For the second trend, the initially established adsorption-desorption equilibrium at the CCR-Pt interface is obviously perturbed by flushing the system with another solvent such as dichloromethane, ethyl acetate, methanol, ethanol, and acetic acid. These trends can already explain the above-mentioned observations made by catalysis researchers, in the sense that the perturbation of initially established adsorption-desorption equilibrium is related to the nature of the solvent. 

The basal spacing (d 001) (DRX-Kristalloflex-805 Siemens) and the surface area (Micromeritics ASAP 2400) was obtained on the solids calcined at different temperatures. X-Ray diffraction patterns have also been obtained after ethylenglycol saturation of selected samples. High resolution transmission electron microscopy (HREM) was performed (Jeol 100 CX Temscan) on ultrathin preparations (LKB Ultratome type 8802A). TPD (NH3) and infrared spectroscopy (pyridine) allowed to evaluate the acid properties of the solid calcined at 4(X) and 600°C. 

Carboxylic acids The smallest carboxylic acid, formic acid, can be measured using infrared spectroscopy (Table 11.2), since it has characteristic absorption bands. As discussed earlier and seen in Fig. 11.33b, mass spectrometry with chemical ionization using SiF5 also revealed HCOOH in an indoor environment (Huey et al., 1998). However, since the sensitivity in these initial studies was about two orders of magnitude less than that for HN03, the detection limit may be about the same as that for FTIR and TDLS. Formic and acetic acids have been monitored continuously from aircraft (Chapman et al., 1995) and their surface flux determined by eddy correlation (Shaw et al., 1998) using atmospheric pressure ionization mass spectrometry. Detection limits are about 30 ppt. 

Here we describe some of the results. In each of these studies, the compound semiconductor was first etched in either acid or base to remove the oxide. The specific surface groups following the etch are not well understood. However, Pluchery et al. have followed the acid etching of InP by in situ infrared spectroscopy [175] and observed the removal of the oxide. Unlike Si, for which an acid (HF) etch leaves the surface hydrogen-terminated and temporarily passivated, acid etching of InP does not produce a chemically passivated surface. Presumably, the surface is left unprotected, and quickly oxidizes if not passivated by another process. Similar results showing reduction or removal of the oxide are seen for GaAs [174,176,177]. 

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