Zeolite Lewis acidity

The structure work consists of synthesizing the faujasite material and characterizing it by X-ray diffraction. The mechanism of the synthesis has been studied and an investigation has been made of the nature of the replacement of the sodium ion by the ammonium ion and of the details of the process of the decomposition of the ammonium ion into the protonic zeolite (Bronsted acid) and decationated zeolite (Lewis acid). (We shall call the material in which the cation has been displaced by a proton and then heated to remove the proton as water, the decationated material.)... 

The rearrangement of styrene oxide can also be performed in liquid-phase reactions with the well known catalyst TS-1 [11,25]. The framework-titanium gives the MFI-type zeolite Lewis acidic properties and 100 % conversion and 98 % phenylacetaldehyde selectivity was achieved after 1-2 h at 70 °C in a batch reaction with acetone (100 mL) as solvent, epoxide (50 g), and catalyst (3 g) as feed. 

It has already been mentioned that cycloaddition across the cyclopropene double bond reduces the ring strain by about 109 kJ/mol. [2+2] cyclo- and -codimerizations of cyclopropenes should therefore be thermodynamically favored processes (see also Sect. 3.2), Indeed, when catalyzed by Zeolites Lewis acids and transition metal complexes onti-tricyclo[3.1.0.0 ]hexane derivatives can be synthesized... 

Electronic structure calculations on the isomerization and epimerization of xylose to xylulose and lyxose by a zeolite Lewis acid catalyst suggest lyxose is formed from a stable intermediate and that xylulose is thermodynamically and kinetically favoured... 

The acidic strength of H-MFl materials is related to the presence of Brpnsted acidic sites whereas, opposite to H-BEA zeolites, Lewis acidic sites represent only a minor feature. 

The next step is the ahstraction of a hydride ion hy a Lewis acid site from the zeolite surface to form the more stable allylic carhocation. This is again followed hy a proton elimination to form a cyclohexadiene intermediate. The same sequence is followed until the ring is completely aromatized. 

Silica gel [11] or alumina [11a, 12] alone, or silica and alumina together modified by Lewis-acid treatment [13] and zeolites [14], have been widely used as catalysts in Diels-Alder reactions, and these solids have also been tested as catalysts in asymmetric Diels-Alder reactions [12,13b,14]. Activated silica gel and alumina at 140 °C were used [15] to catalyze the asymmetric cycloaddition of (-)-menthyl-N-acetyl-a, S-dehydroalaninate (3) (R = NHCOMe) with cyclopentadiene in the key step for synthesizing optically active cycloaliphatic a-amino acids. When the reactions were carried out in the absence of solvent, a higher conversion was obtained. Some results are reported in Table 4.5 and compared with those obtained by using silica and alumina modified by treatment with Lewis acids. Silica gel gives a reasonable percentage of conversion after 24 h with complete diastereofacial selectivity in exo addition. 

Good yields and high diastereoselectivities were obtained by using zeolites in combination with Lewis-acid catalyst [21]. Table 4.7 illustrates some examples of Diels-Alder reactions of cyclopentadiene, cyclohexadiene and furan with methyl acrylate. Na-Y and Ce-Y zeolites gave excellent results for the cycloadditions of carbocyclic dienes, and combining these zeolites with anhydrous ZnBr2 further enhanced the endo diastereoselectivity of the reaction. An exception is the cycloaddition of furan that occurred considerably faster and with better yield, in comparison with the classic procedure [22], when performed in the presence of sole zeolites. 

Zeolite and Lewis-acid catalysis in Diels-Alder reactions of isoprene [20b]... 

The previous sections have shown that desihcation of ZSM-5 zeohtes results in combined micro- and mesoporous materials with a high degree of tunable porosity and fuUy preserved Bronsted acidic properties. In contrast, dealumination hardly induces any mesoporosityin ZSM-5 zeolites, due to the relatively low concentration of framework aluminum that can be extracted, but obviously impacts on the acidic properties. Combination of both treatments enables an independent tailoring of the porous and acidic properties providing a refined flexibility in zeolite catalyst design. Indeed, desihcation followed by a steam treatment to induce dealumination creates mesoporous zeolites with extra-framework aluminum species providing Lewis acidic functions [56]. 

Figure 3 shows 13c MAS spectra of acetone-2-13c on various materials. Two isotropic peaks at 231 and 227 ppm were observed for acetone on ZnCl2 powder, and appreciable chemical shift anisotropy was reflected in the sideband patterns at 193 K. The 231 ppm peak was in complete agreement with the shift observed for acetone diffused into ZnY zeolite. A much greater shift, 245 ppm, was observed on AICI3 powder. For comparison, acetone has chemical shifts of 205 ppm in CDCI3 solution, 244 ppm in concentrated H2SO4 and 249 ppm in superacid solutions. The resonance structures 5 for acetone on metal halide salts underscore the similarity of the acetone complex to carbenium ions. The relative contributions of the two canonical forms rationalizes the dependence of the observed isotropic 13c shift on the Lewis acidity of the metal halide. 

The catalytic activity for NO oxidation [reaction(l)] was strongly inhibited by water vapor, because this reaction occurs on Lewis acid sites of zeolite as... 

While our discussion will mainly focus on sifica, other oxide materials can also be used, and they need to be characterized with the same rigorous approach. For example, in the case of meso- and microporous materials such as zeolites, SBA-15, or MCM materials, the pore size, pore distribution, surface composition, and the inner and outer surface areas need to be measured since they can affect the grafting step (and the chemistry thereafter) [5-7]. Some oxides such as alumina or silica-alumina contain Lewis acid centres/sites, which can also participate in the reactivity of the support and the grafted species. These sites need to be characterized and quantified this is typically carried out by using molecular probes (Lewis bases) such as pyridine [8,9],... 

Another major cause of waste is the use of mineral acids (H2SO4, H3PO4, etc.) and Lewis acids (AICI3, ZnCL), often in stoichiometric amounts, which cannot be recovered and recycled. A typical example is the HNO3/H2SO4 mixture used in aromatic nitrations. Consequently, there is a discernible trend towards the use of solid, recyclable Brpnsted and Lewis acids, e.g. zeolites, acidic clays, etc. (see later) as alternatives to conventional mineral and Lewis acids. 

Many standard reactions that are widely applied in the production of fine chemicals employ. strong mineral or Lewis acids, such as sulphuric acid and aluminium chloride, often in stoichiometric quantities. This generates waste streams containing large amounts of spent acid, which cannot easily be recovered and recycled. Replacement of these soluble mineral and Lewis acids by recyclable. solid acids, such as zeolites, acid clays, and related materials, would represent a major breakthrough, especially if they functioned in truly catalytic quantities. Consequently, the application of solid acids in fine chemicals synthesis is currently the focus of much attention (Downing et al., 1997). 

Figure 3.53. IR transmission absorption spectrum of pyridine adsorbed on partly dehydroxylated HY zeolite (Van Bekkum et al, 1991) B = Bronsted acid sites L = Lewis acid sites.

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. 

Traditionally, the production of LABs has been practiced commercially using either Lewis acid catalysts, or liquid hydrofluoric acid (HF).2 The HF catalysis typically gives 2-phenylalkane selectivities of only 17-18%. More recently, UOP/CEPSA have announced the DetalR process for LAB production that is reported to employ a solid acid catalyst.3 Within the same time frame, a number of papers and patents have been published describing LAB synthesis using a range of solid acid (sterically constrained) catalysts, including acidic clays,4 sulfated oxides,5 plus a variety of acidic zeolite structures.6"9 Many of these solid acids provide improved 2-phenylalkane selectivities. 

The amount of Lewis acid to be used is depicted as an effective amount and a minimum limit of 0.5 mole equivalent with respect to the sulfmated compound concentration was mentioned. A wide variety of Lewis acids was mentioned to be useful for the present invention in the patent document, but only copper (II) compounds were claimed. The way in which the Lewis acid is used (either as a homogeneous or a heterogeneous phase), was reported to be irrelevant. So, it could be employed in solution in the reaction medium or insoluble as powders or on a solid support, such as alumina or a zeolite. The Lewis acid is supposed to be acting as a catalyst in the desulfination process. The temperature and pressure conditions for this reaction are substantially higher than the microbial conditions. The temperature and pressure conditions did not form part of any claim, but the document stipulates values between 50°C and 100°C, and 10 and 15psi, respectively. The quantitative effectiveness or conversion values of this reaction were not given, but it looks like it would diminish the advantages of a biocatalytic process. 

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... 

Adsorption enthalpies and vibrational frequencies of small molecules adsorbed on cation sites in zeolites are often related to acidity (either Bronsted or Lewis acidity of H+ and alkali metal cations, respectively) of particular sites. It is now well accepted that the local environment of the cation (the way it is coordinated with the framework oxygen atoms) affects both, vibrational dynamics and adsorption enthalpies of adsorbed molecules. Only recently it has been demonstrated that in addition to the interaction of one end of the molecule with the cation (effect from the bottom) also the interaction of the other end of the molecule with a second cation or with the zeolite framework (effect from the top) has a substantial effect on vibrational frequencies of the adsorbed molecule [1,2]. The effect from bottom mainly reflects the coordination of the metal cation with the framework - the tighter is the cation-framework coordination the lower is the ability of that cation to bind molecules and the smaller is the effect on the vibrational frequencies of adsorbed molecules. This effect is most prominent for Li+ cations [3-6], In this contribution we focus on the discussion of the effect from top. The interaction of acetonitrile (AN) and carbon monoxide with sodium exchanged zeolites Na-A (Si/AM) andNa-FER (Si/Al= 8.5 and 27) is investigated. 

The effect of crystal size of these zeolites on the resulted toluene conversion can be ruled out as the crystal sizes are rather comparable, which is particularly valid for ZSM-5 vs. SSZ-35 and Beta vs. SSZ-33. The concentrations of aluminum in the framework of ZSM-5 and SSZ-35 are comparable, Si/Al = 37.5 and 39, respectively. However, the differences in toluene conversion after 15 min of time-on-stream (T-O-S) are considerable being 25 and 48.5 %, respectively. On the other hand, SSZ-35 exhibits a substantially higher concentration of strong Lewis acid sites, which can promote a higher rate of the disproportionation reaction. Two mechanisms of xylene isomerization were proposed on the literature [8] and especially the bimolecular one involving the formation of biphenyl methane intermediate was considered to operate in ZSM-5 zeolites. Molecular modeling provided the evidence that the bimolecular transition state of toluene disproportionation reaction fits in the channel intersections of ZSM-5. With respect to that formation of this transition state should be severely limited in one-dimensional (1-D) channel system of medium pore zeolites. This is in contrast to the results obtained as SSZ-35 with 1-D channels system exhibits a substantially higher... 

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