Adsorption IR spectroscopy

A munber of studies have been addressed to define the location and nature of the active species [2,5], Likewise, the assessment of textural and chemical properties induced by the exchanged cations becomes crucial to the understanding of the applicability of these materials in a given process. A large variety of methods can be used to evaluate these surface properties. Among them, N2 adsorption, IR spectroscopy and adsorption of probe molecules are widely used. 

Dietzel PDC, lohnsen RE, FjeUvag H et al (2008) Adsorption properties and structure of CO2 adsorbed on open coordination sites of metal-organic framework Niaidhtp) from gas adsorption, IR spectroscopy and X-ray diffraction. Chem Commun 41 5125-5127... 

There have been a few other experimental set-ups developed for the IR characterization of surfaces. Photoacoustic (PAS), or, more generally, photothemial IR spectroscopy relies on temperature fluctuations caused by irradiating the sample with a modulated monocliromatic beam the acoustic pressure wave created in the gas layer adjacent to the solid by the adsorption of light is measured as a fiinction of photon wavelength... 

The use of CO is complicated by the fact that two forms of adsorption—linear and bridged—have been shown by infrared (IR) spectroscopy to occur on most metal surfaces. For both forms, the molecule usually remains intact (i.e., no dissociation occurs). In the linear form the carbon end is attached to one metal atom, while in the bridged form it is attached to two metal atoms. Hence, if independent IR studies on an identical catalyst, identically reduced, show that all of the CO is either in the linear or the bricked form, then the measurement of CO isotherms can be used to determine metal dispersions. A metal for which CO cannot be used is nickel, due to the rapid formation of nickel carbonyl on clean nickel surfaces. Although CO has a relatively low boiling point, at vet) low metal concentrations (e.g., 0.1% Rh) the amount of CO adsorbed on the support can be as much as 25% of that on the metal a procedure has been developed to accurately correct for this. Also, CO dissociates on some metal surfaces (e.g., W and Mo), on which the method cannot be used. 

The versatile IR method may be extended to extremes of both temperature and pressure as a probe of adsorption and reaction processes on surfaces. The extension of IR spectroscopy to the study of weakly-bound surface species at low temperatures opens up the possibility of stabilization of transient surface species which are Involved in surface chemistry at high temperatures. 

However, the comparison of the whole series of experimental facts involving IR-spectroscopy of adsorption of molecular and atomic hydrogen as well as the change in electric conductivity of adsorbent is indicative of a more complex phenomenon. For instance, in paper [97] both the spectra of adsorption of adsorbed molecular hydrogen were studied together with those of hydrogen atoms adsorbed from gaseous phase. In case when H2 are adsorbed in a dissociative manner one would have expected a manifestation of the same bands 3498 and 1708 cm or at least one of them inherent to adsorption of H-atoms in the spectrum of ZnO. 

N.N. Savvin, Mechanism of Adsorption of Atoms, Radicals and Some Simple Molecules on Metal Oxides According to the Data on Electroconductivity and IR-spectroscopy, PhD (Chemistry) Thesis, Moscow, 1980... 

Note that, unfortunately, the authors of [63] did not study adsorption of hydrogen atoms from gas phase by IR spectroscopy. However, this investigation was carried out in [64], The results obt ned in these experiments confirm the above notion of the process. 

Vibrational spectroscopy provides the most definitive means of identifying the surface species arising from molecular adsorption and the species generated by surface reaction, and the two techniques that are routinely used for vibrational studies of molecules on surfaces are Infrared (IR) Spectroscopy and Electron Energy Loss Spectroscopy (HREELS) (q.v.). 

Montanari el al., for example, studied a Co—H-MFI sample through FT-IR spectroscopy of in situ adsorption and coadsorption of probe molecules [o-toluonitrile (oTN), CO and NO] and CH4-SCR process tests under IR operando conditions. The oTN adsorption and the oTN and NO coadsorption showed that both Co2+ and Co3+ species are present on the catalyst surface. Co3+ species are located inside the zeolitic channels while Co2+ ions are distributed both at the external and at the internal surfaces. The operando study showed the activity of Co3+ sites in the reaction. The existence of three parallel reactions, CH4-SCR, CH4 total oxidation and NO to NOz oxidation, was also confirmed. Isocyanate species and nitrate-like species appear to be intermediates of CH4-SCR and NO oxidation, respectively. A mechanism for CH4-SCR has been proposed. On the contrary, Co2+ substitutional sites, very evident and predominant in the catalyst, which are very hardly reducible, seemed not to play a key role in the SCR process [173],... 

IR investigations of methanol oxidation have been mainly devoted to demonstrate the nature of strongly adsorbed residues produced during the adsorption of methanol [21,59,67,68], Bulk oxidation products were not investigated by in situ IR spectroscopy. 

It must be acknowledged, however, that the determination of the number of the different surface species which are formed during an adsorption process is often more difficult by means of calorimetry than by spectroscopic techniques. This may be phrased differently by saying that the resolution of spectra is usually better than the resolution of thermograms. Progress in data correction and analysis should probably improve the calorimetric results in that respect. The complex interactions with surface cations, anions, and defects which occur when carbon monoxide contacts nickel oxide at room temperature are thus revealed by the modifications of the infrared spectrum of the sample (75) but not by the differential heats of the CO-adsorption (76). Any modification of the nickel-oxide surface which alters its defect structure produces, however, a change of its energy spectrum with respect to carbon monoxide that is more clearly shown by heat-flow calorimetry (77) than by IR spectroscopy. 

Using only IR spectroscopy, it seems very difficult to correlate the different peaks together because they all appear or disappear at the same time and a lot of experiments are necessary to make a conclusion. Hence, 2D correlation was applied to infrared spectra obtained during CO adsorption. The interest of this technique is that only one experiment is needed to obtain the desired result. 

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