NH3 adsorption

The results of work [ 135] are of specific interest. The work surveyed the influence of the nature and structure of adsorbed layers upon the mechanism of deactivation of He(2 S) atoms. It has been shown that on a surface of pure Ni(lll) coated with absorbed bridge-positioned molecules of CO or NO, the deactivation of metastable atoms proceeds by the mechanism of resonance ionization with subsequent Auger-neutralization. With large adsorbent coverages, when the adsorbed molecules are in a position normal to the surface, deactivation proceeds by the one-electron Auger-mechanism. The adsorbed layers of C2H4 and H2O on Ni(lll) de-excite atoms of He(2 S) by the two-electron mechanism solely. In case of NH3 adsorption, both mechanisms of deactivation are simultaneously realized. Based on the given data, the authors infer that the nature of metastable atoms deactivation on an adsorbate coated metal surface is determined by the distance the electron density of adsorbate valance electrons is removed from the metal lattice. 

Analysis of the dynamics of SCR catalysts is also very important. It has been shown that surface heterogeneity must be considered to describe transient kinetics of NH3 adsorption-desorption and that the rate of NO conversion does not depend on the ammonia surface coverage above a critical value [79], There is probably a reservoir of adsorbed species which may migrate during the catalytic reaction to the active vanadium sites. It was also noted in these studies that ammonia desorption is a much slower process than ammonia adsorption, the rate of the latter being comparable to that of the surface reaction. In the S02 oxidation on the same catalysts, it was also noted in transient experiments [80] that the build up/depletion of sulphates at the catalyst surface is rate controlling in S02 oxidation. 

Elanany, M., Koyama, M., Kubo, M. el al. (2005) Periodic density functional investigation of Lewis acid sites in zeolites Relative strength order as revealed from NH3 adsorption, Appl. Surf. Sci., 246, 96. 

Temperature programmed desorption (TPD) of NH3 adsorbed on the samples was carried out on an Altamira TPD apparatus. NH3 adsorption was performed at 50°C on the sample that had been heat-treated at 120°C in a helium flow. After flushing with helium, the sample was subjected to TPD from 50 to 600°C (AT = 10°C min 1). The evolved NH3, H20 and N2 were monitored by mass spectroscopy by recording the mass signals of m/e = 16, 18 and 28, respectively using a VG Trio-1 mass spectrometer. 

XPS of NH3 adsorption was carried out on a SSI (Surface Science Instrument) spectrometer. NH3 was adsorbed at 80 °C on the calcined samples and then outgassed under helium at 350 °C. The proportion of each type of site (Bronsted and Lewis) was evaluated by analyzing the Nls band. 

Table 2. Acidic properties of the samples based on NH3 adsorption at 80°C and pyridine adsorption at 150°C, respectively.

Bolis et al (43) reported volumetric data characterizing NH3 adsorption on TS-1 that demonstrate that the number of NH3 molecules adsorbed per Ti atom under saturation conditions was close to two, suggesting that virtually all Ti atoms are involved in the adsorption and have completed a 6-fold coordination Ti(NH3)204. The reduction of the tetrahedral symmetry of Ti4+ ions in the silicalite framework upon adsorption of NH3 or H20 is also documented by a blue shift of the Ti-sensitive stretching band at 960 cm-1 (43,45,134), by a decrease of the intensity of the XANES pre-edge peak at 4967 eV (41,43,134), and by the extinction of the resonance Raman enhancement of the 1125 cm-1 band in UV-Raman spectra (39,41). As an example, spectra in Figs. 15 and 16 show the effect of adsorbed water on the UV-visible (Fig. 15), XANES (Fig. 16a), and UV-Raman (Fig. 16b) spectra of TS-1. 

Figure 5 Variations with coverage of the differential heats of NH3 adsorption at 143°C on H-ZSM-5 sample not men-tionned in table 1...

Ammonia and pyridine are frequently used as probe molecules for the characterization of acidic surfaces, but they also adsorb on strongly basic sites. Tsyganenko et al. (54) proposed various species resulting from NH3 adsorption on basic solids (Scheme 1). The formation of species I corresponds to hydrogen bonding to a basic surface oxygen, and species II, formed by dissociation to give NH2 and hydroxyl species, involves an acid-base site. Such adsorption requires... 

To describe the NH3 + NO + O2 (standard SCR) reacting system, NH3 adsorption-desorption, ammonia oxidation to nitrogen and standard SCR have been considered with the kinetics already presented in the previous section. 

Bulk boron oxide was found to be much more acidic than basic [168], When SO2 adsorption microcalorimetry was used, no basic sites were observed, but some phy-sisorption occurred. Ammonia and pyridine adsorption microcalorimetry were used to characterize the acidity of B2O3. Boron oxide displays an initial heat for NH3 adsorption of 80 kJ/mol and can adsorb irreversibly a large amount of ammonia. The number of active sites determined by pyridine adsorption and the corresponding integral heats were found to be much lower than those determined by using ammonia. 

The amphoteric indium oxide can be considered as more basic than acidic when comparing the adsorption heats and irreversible adsorbed amounts, which are clearly higher for SO2 adsorption than for ammonia adsorption [40,47]. The heats of NH3 adsorption decreased continuously with coverage, while the SO2 adsorption heat remained constant over a wide range of coverage. 

The microcalorimetry of NH3 adsorption coupled with infrared spectroscopy was used to study the effect of the synthesis medium (OH or F ) on the nature and amount of acid sites present in Al,Si-MFl zeolites [103]. Both techniques revealed that H-MFl (F ) with Si/Al < 30 contained extra-framework aluminum species. Such species were responsible for the presence of Lewis acid sites and poisoning of the Brpnsted acidity. In contrast, MFl (F ) characterized by Si/Al > 30 presented the same behavior as H-MFl (OH ). 

The acidic/basic properties of zeolites can be changed by introdnction of B, In, Ga elements into the crystal framework. For example, a coincorporation of alnminnm and boron in the zeolite lattice has revealed weak acidity for boron-associated sites [246] in boron-snbstitnted ZSM5 and ZSMll zeolites. Ammonia adsorption microcalorimetry gave initial heats of adsorption of abont 65 kJ/mol for H-B-ZSMll and showed that B-substituted pentasils have only very weak acidity [247]. Calcination at 800°C increased the heats of NH3 adsorption to about 170 kJ/mol by creation of strong Lewis acid sites as it can be seen in Figure 13.13. The lack of strong Brpnsted acid sites in H-B-ZSMll was confirmed by poor catalytic activity in methanol conversion and in toluene alkylation with methanol. 

Microcalorimetric experiments of NH3 adsorption have shown that the isomor-phous substitution of A1 with Ga in various zeolite frameworks (offretite, faujasite, beta) leads to reduced acid site strength, density, and distribution [250,252,253], To a lesser extent, a similar behavior has also been observed in the case of a MFI framework [51,254]. A drastic reduction in the acid site density of H,Ga-offretites has been reported, while the initial acid site strength remained high [248,250]. 

The reactions take place only in active catalytic layer, the rates Rj are considered individually for each type of the converter (DOC, SCR, NSRC, TWC). The development of suitable reaction schemes and the evaluation of kinetic parameters are discussed generally in Section IV. The details for DOC, NSRC and SCR of NOx by NH3 are given in Sections V, VI and VII, respectively. The important species deposited on the catalyst surface are balanced (e.g. HC adsorption in DOC, oxygen and NOx storage in NSRC, NH3 adsorption in SCR). Heat transfer by radiation and homogeneous reactions... 

On increasing the adsorption temperature, shorter dead-times are observed in Fig. 35 (respectively 280, 220, 190 and 140 s for rads = 50, 100, 150 and 200°C) thus the amount of NH3 adsorbed onto the catalyst surface is reduced, in line with the exothermic NH3 adsorption process. Likewise the TPD runs, whose areas decrease on increasing the adsorption temperature, also confirm the lower storage capacity of the system at higher temperatures. 

Based on literature indications (Lietti et al., 1997, 2000) and supported by preliminary fits of the experimental data, a non-activated NH3 adsorption process and Temkin-type NH3 desorption kinetics have been assumed, i.e. 

The following reactions were included in the kinetic model NH3 adsorption (R3 in Table V), NH3 desorption (R4 in Table IV), NH3 oxidation (R5 in Table IV) and standard SCR (R6 in Table V). Mass balances for adsorbed ammonia and nitrogen now include the standard SCR reaction. Moreover, the mass balance of gaseous NO was introduced, too... 

The MR rate law relies on the assumption that the SCR reaction is governed by a redox mechanism and therefore predicts a kinetic dependence on oxygen. It has been derived assuming that (i) two types of sites for NH3 adsorption (acidic non-reducible sites) and for NO + NH3 activation/reaction (redox sites, associated with vanadium), respectively, prevail on the catalyst surface (ii) NH3 blocks the redox sites (iii) reoxidation of the redox sites is rate controlling. 

Consistently with what reported in the previous sections the NH3 adsorption, desorption and oxidation rates were fitted by the following expressions, respectively ... 

Reversible transition of penta- and octahedrally coordinated Al species into tetrahedral Al after hydrothermal treatment is confirmed by FTIR measurements of NH3 adsorption/desorption. They show a reformation of Bronsted sites. The concentration of BS rises to 50% and more with respect to the initial value. This reformation of BS can be explained by an re-hydroxylation of the internal surface. 

Figure 17.11 Diffuse reflectance FTIR spectra of NH3 adsorption of 12.5% Mo03/AI203 at...

NH3 is similar to H2O in that they both possess large dipole moments and are both small molecules. The presence of NH3 in a zeolite is chemically similar to the presence of H2O in a zeolite. Therefore, the hydrated cation distribution in zeolites is probably more typical of NH3 adsorption in zeolites than the dehydrated cation distribution. According to Breck (18), for hydrated zeolite X, cations are found in sites SI, SI, SII, and SIV. Of these sites, SI, SII, and SIV would all be adsorption lattice solution sites. The cationic and anionic lattice solution sites (in the supercavity of NaX) are illustrated in Figure 8. For NH3, the subscript J1 will refer to SII sites, the subscript J2 will refer to SI sites, and J3 will refer to SIV sites. The anionic sites are two and are (l) in the center U-membered ring of the connecting frame and (2) near the center of the 0(2)—0(1)—0(l) triad of oxygen atoms. For NH3, the subscript il will refer to the first anionic site the subscript i2 will refer to the second anionic site. 

Reduction of Nitric Oxide with Ammonia. - Control of the emission of NO from stationary sources is possible by selective catalytic reduction, for which up to now NH3 is the only effective reductant in the presence of excess 02. Beside noble metal catalysts Bauerle etal.101 109 and Wu and Nobe108 studied Al2 03-supported vanadium oxide and found this to be highly effective in NO removal which is considerably enhanced by the presence of 02. Alkali metal compounds which are usually added as promoters for S02 oxidation completely inactivate the catalysts for NO reduction. Adsorption kinetic studies indicated first-order dependence on NH3 adsorption. Similar results were obtained for NO on reduced vanadium oxide, but its adsorption on... 

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