Lewis sites zeolites

It must be noted that sometimes calcination is beneficial to create active species. Notable examples are the Sn-beta speciation [176] and generation of extra-framework Al-Lewis sites in beta zeolite for organic transformations... 

Spectroscopy. In the methods discussed so far, the information obtained is essentially limited to the analysis of mass balances. In that re.spect they are blind methods, since they only yield macroscopic averaged information. It is also possible to study the spectrum of a suitable probe molecule adsorbed on a catalyst surface and to derive information on the type and nature of the surface sites from it. A good illustration is that of pyridine adsorbed on a zeolite containing both Lewis (L) and Brbnsted (B) acid sites. Figure 3.53 shows a typical IR ab.sorption spectrum of adsorbed pyridine. The spectrum exhibits four bands that can be assigned to adsorbed pyridine and pyridinium ions. Pyridine adsorbed on a Bronsted site forms a (protonated) pyridium ion whereas adsorption on a Lewis site only leads to the formation of a co-ordination complex. 

Low temperature CO sorption experiments monitored with the IR spectroscopy were used to determine the nature of active (acid) sites present in the Fe-TON zeolites. It is well known that CO is a useful probe molecule for Lewis acid sites. Narrow and well resolved bands appear in the region 2135 - 2150 cm"1. The IR spectra of CO sorbed in amount sufficient to cover all Lewis sites in the Fe-TON of different Si/Fe ratios are presented in Figure 2A. The samples of a high iron content (Si/Fe=27, 36) showed a significantly lower thermal stability. The activation of the NFL form of these Fe-TON... 

Figure 2. (A) IR spectra of CO adsorbed on the Fe-TON zeolites of different Si/Fe ratio at very low CO coverage required for the detection of the Lewis sites., (B) Difference spectra of CO adsorbed on Fe-TON of different Si/Fe ratio recorded upon the saturation of all Bronsted sites.

SSZ-35 the reactions would be influenced by the presence of very strong Lewis sites. Quantitative sorption of ammonia, pyridine and d3-acetonitrile in both zeolites showed that the real number of acidic groups was close to values, derived form the number of aluminum atoms (taken from AAS analysis) in the idealized unit cell. Obtained values are 1.1 H+/u.c. for SSZ-33 with idealized unit cell composition H2.9[Al2.9Si53.iOii2] (plus 1.3 Lewis sites per u.c.) and 0.3 H+/u.c. for SSZ-35 with ideal formula Ho.4[Alo.4Sii5 6032] (plus 0.05 Lewis sites per u.c.). 

It is generally admitted that over zeolites, acetylation of aromatic substrates with acetic anhydride (AA) is catalyzed by protonic acid sites. The direct participation of Lewis sites was excluded by using two BEA samples with similar protonic acidities, but with very different Lewis acidities indeed, these samples were shown to have quasi-similar activities. The currently accepted mechanism is shown in Figure 12.6 for the anisole acetylation example. The limiting step of the process is the attack of anisole molecules by acylium ions. 

As mentioned above, an acidic zeolite can provide both protonic (Bronsted) and aprotonic (Lewis) sites. The Bronsted sites are typically structural or surface hydroxyl groups and the Lewis sites can be charge compensating cations or arise from extra-framework aluminum atoms. A basic (proton acceptor) molecule B will react with surface hydroxyl groups (OH ) via hydrogen bonding... 

It is generally accepted that Lewis acidity in zeolites is due mainly to extraframework aluminum (16,17,18). Consequently, Lewis acid sites measured by pyridine adsorption must correlate with extra-framework aluminum. In Table I, the amount of pyridine coordinated to Lewis sites decreases for samples with the lowest Si/Al ratio, showing that, after thermal treatment, the amount of extraframework aluminum decreases with Si/Al ratio of the Beta zeolite. 

NMR has been extensively applied to carbonyl compounds in acidic zeolites and other solid acids. The unshared pairs of electrons on the oxygen can interact with either Brpnsted or Lewis sites, and aldol condensation reactions are commonly observed. Acetone was first studied on a zeolite by Bosacek and co-workers (146) followed by Haw and co-workers (147) and later by Gorte and co-workers (148). The conclusion of an earlier acetone paper of Gorte and co-workers (149) was that acetone forms a static complex on the Brdnsted site of HZSM-5 at room temperature, but this claim was later revised (150) upon the realization that molecular motion in the complex is not halted except at appreciably lower temperatures. 

Ellis and co-workers published a 13C MAS study of ethylamine on solid acids in 1981 (157). Maciel and Haw (158, 159) published NMR studies of pyridine as a probe molecule on solid acids in 1983. We have recently begun to reexamine the 15N spectrum of pyridine on zeolites and other solid acids (160). At low temperatures pyridine is remarkably sensitive to the kinds of acid sites present. Figure 28 shows 15N spectra of pyridine adsorbed on HY samples before and after dealumination. Dealumination in this case seems to make four kinds of Lewis sites distinguishable by NMR of adsorbed pyridine, suggesting pyridine as a good candidate for... 

Fig. 28. 36-MHz l5N CP/MAS spectra of pyridine-15N on zeolite HY. The experimental conditions were all the same for (a) and (b), except that sample b was extensively dealuminated by increasing the activation temperature to SSITC (400°C for sample a). Both spectra were acquired at 77 K to prevent chemical exchanges on the NMR time scale, (a) The single resonance at —176 ppm as well as its associated sidebands indicates protonation of pyridine by the Brpnsted sites, (b) In addition to the protonated pyridine, four additional resonances at -68, -88, —116, and -140 ppm are also seen, indicating complexation of pyridine with different extraframework Lewis sites.

The thermal stability of NH4Y zeolite in which ammonium ions have been exchanged at various levels with La3+ ions was studied. The catalytic activity of these La zeolites in isooctane cracking was measured as a function of pretreatment temperature, and an IR study of the chemisorption of pyridine was used to determine the numbers of Bronsted and Lewis sites. The structural damage resulting from high temperature calcination was examined qualitatively. 

C is constant on the three La zeolites heated at 900° C in dry air whereas the number of Lewis sites decreases with increasing La content. The Na-8.7 sample heated at 900° C in dry air has no acidity. Accordingly, the Bronsted and Lewis acid sites on the Na-8.7 sample heated at only 800° C are plotted in Figure 3 for comparison with the 900°C-pretreated La zeolites. The plots indicate that the introduction of La3+ ions in the lattice increases the number of Bronsted sites even for a higher temperature... 

The nature of the surface acidity is dependent on the temperature of activation of the NH4-faujasite. With a series of samples of NH4—Y zeolite calcined at temperatures in the range of 200° to 800°C, Ward 148) observed that pyridine-exposed samples calcined below 450°C displayed a strong infrared band at 1545 cm-1, corresponding to pyridine bound at Brpnsted (protonic) sites. As the temperature of calcination was increased, the intensity of the 1545-cm 1 band decreased and a band appeared at 1450 cm-1, resulting from pyridine adsorbed at Lewis (dehydroxylated) sites. The Brtfnsted acidity increased with calcination temperature up to about 325°C. It then remained constant to 500°C, after which it declined to about 1/10 of its maximum value (Fig. 19). The Lewis acidity was virtually nil until a calcination temperature of 450°C was reached, after which it increased slowly and then rapidly at calcination temperatures above 550°C. This behavior was considered to be a result of the combination of two adjacent hydroxyl groups followed by loss of water to form tricoordinate aluminum atoms (structure I) as suggested by Uytterhoeven et al. 146). Support for the proposed dehydroxylation mechanism was provided by Ward s observations of the relationship of Brpnsted site concentration with respect to Lewis site concentration over a range of calcination tem-... 

Evidence that something more than a proper Alf distribution is needed to create strong acidity first came from the experiments of Beyerlein et al. (7). Using the acid-catalyzed conversion of isobutane as a measure of strong acidity, they found that a dealuminated zeolite prepared by treatment with ammonium hexafluorosilicate (AHF) exhibited much less carbonium ion activity than might be expected, based on the number of Alf atoms. This treatment leaves very little extraframework Al in the zeolite. When the sample was mildly steamed, the activity became considerably greater. The authors concluded that the enhanced acidity was a result of a synergism between the framework Bronsted sites and the Lewis sites associated with extraframework aluminum. 

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