Diquaternary Ammonium Compounds in Zeolite Synthesis: Cyclic and Polycyclic N-Heterocycles Connected by Methylene Chains

An additional dimension has been added to our long-standing studies in high silica zeolite synthesis via a guest/host synergism. We have created and studied the impact of making symmetric diquaternary ammonium compounds, by varying the chain length between nitrogen charge centers, and the heterocycle size and geometry containing the nitrogen. This allows the introduction of a second spatial parameter in the use of the charged organo-cation guest in the zeolite synthesis. The series of 15 diquaternary ammonium compounds (5 heterocycles synthesized onto chain lengths of C4−C6) were tested in a total of 135 zeolite syntheses reactions. Nine screening reactions were employed for each guest molecule, and the conditions built upon past successes in finding novel high silica zeolites via introduction of boron, aluminum, or germanium as substituting tetrahedral framework atoms for silicon. Eighteen different zeolite structures emerged from the studies. The use of specific chain lengths for derivatives of the pyrrolidine ring system produced novel zeolite materials SSZ-74 and 75

Nonaqueous Fluoride/Chloride Anion-Promoted Delamination of Layered Zeolite Precursors: Synthesis and Characterization of UCB-2

The delamination of layered zeolite precursor PREFER is demonstrated under mild nonaqueous conditions using a mixture of cetyltrimethylammonium bromide, tetrabutylammonium fluoride, and tetrabutylammonium chloride in N,N-dimethylformamide (DMF) as solvent. The delamination proceeds through a swollen material intermediate which is characterized using powder X-ray diffraction (PXRD). Subsequent addition of concentrated HCl at room temperature leads to synthesis of UCB-2 via delamination of the swollen PREFER material and is characterized using PXRD, transmission electron microscopy (TEM), and argon gas physisorption, which shows lack of microporosity in UCB-2. ^(29)Si magic angle spinning (MAS) NMR spectroscopy indicates lack of amorphization during delamination, as indicated by the entire absence of Q^2 resonances, and ^(27)Al MAS NMR spectroscopy shows exclusively tetrahedral aluminum in the framework following delamination. The delamination process requires both chloride and fluoride anions and is sensitive to solvent, working well in DMF. Experiments aimed at synthesizing UCB-2 using aqueous conditions previously used for UCB-1 synthesis leads to partial swelling and lack of delamination upon acidification. A similar lack of delamination is observed upon attempting synthesis of UCB-1 under conditions used for UCB-2 synthesis. The delamination of PREFER is reversible between delaminated and swollen states in the following manner. Treatment of as-made UCB-2 with the same reagents as used here for the swelling of PREFER causes the delaminated UCB-2 material to revert back to swollen PREFER. This causes the delaminated UCB-2 material to revert back to swollen PREFER. Altogether, these results highlight delamination as the reverse of zeolite synthesis and demonstrate the crucial role of noncovalent self-assembly involving the zeolitic framework and cations/anions/structure-directing agent and solvent during the delamination process

Delamination of Layered Zeolite Precursors under Mild Conditions: Synthesis of UCB-1 via Fluoride/Chloride Anion-Promoted Exfoliation

New material UCB-1 is synthesized via the delamination of zeolite precursor MCM-22 (P) at pH 9 using an aqueous solution of cetyltrimethylammonium bromide, tetrabutylammonium fluoride, and tetrabutylammonium chloride at 353 K. Characterization by powder X-ray diffraction, transmission electron microscopy, and nitrogen physisorption at 77 K indicates the same degree of delamination in UCB-1 as previously reported for delaminated zeolite precursors, which require a pH of greater than 13.5 and sonication in order to achieve exfoliation. UCB-1 consists of a high degree of structural integrity via ^(29)Si MAS NMR and Fourier transform infrared spectroscopies, and no detectable formation of amorphous silica phase via transmission electron microscopy. Porosimetry measurements demonstrate a lack of hysteresis in the N_2 adsorption/desorption isotherms and macroporosity in UCB-1. The new method is generalizable to a variety of Si:Al ratios and leads to delaminated zeolite precursor materials lacking amorphization

Physicochemical Properties and Catalytic Behavior of the Molecular Sieve SSZ-70

SSZ-70 is synthesized using 1,3-bis(isobutyl)imidazolium, 1,3-bis(cyclohexyl)imidazolium, and 1,3-bis(cycloheptyl)imidazolium structure directing agents (SDAs), and the solids obtained are characterized by powder X-ray diffraction (XRD), ^(29)Si magic angle spinning nuclear magnetic resonance (MAS NMR), electron microscopy, nitrogen and hydrocarbon adsorption, and thermogravimetric analyses. The physicochemical properties of SSZ-70 show that it is a new molecular sieve that has similarities to MWW-type materials. The catalytic behavior of SSZ-70 is evaluated through the use of the constraint index (CI) test. Distinct differences in the reactivity between Al-SSZ-70 and SSZ-25 (MWW) are observed and are the consequences of the structural differences between these two molecular sieves

Studies of Aluminum Reinsertion into Borosilicate Zeolites with Intersecting Channels of 10- and 12-Ring Channel Systems

The work here describes the kinetic analyses of aluminum replacement for boron in a suite of borosilicate molecular sieves. While the method has been described before as a means of converting synthesized borosilicates (with weak inherent acidity) to aluminosilicates (with much stronger acid strength) when there are large pores in the structure, here we carry out the transformation under less than optimal replacement concentrations, in order to better follow the kinetics. We examined several zeolite structures with boundary conditions of boron MEL where there are only 10-ring (or intermediate) pore structures and no Al is taken up, to multidimensional large pore zeolites, like boron beta, where Al substitution can occur everywhere. We also studied materials with both intermediate and large pores, SSZ-56, 57, 70, and 82. In the case of 57 up to 90% of the structure is made up of boron MEL. We observe that the pH drop is proportional to the Al reinsertion and is the same for all zeolites we studied. In one case, we compared a zeolite (SSZ-24) with boron and then no boron sites and found that Al does not go into defect sites. It was again confirmed (shown in earlier work) that Al will go into nest sites created by boron hydrolysis out of the substrate before Al treatment. Along those lines we also made two new observations: (1) the profile for Al uptake, as followed by pH drop, is the same kinetically, whether the boron is there or not; and (2) NMR showed that the boron is leaving the structure faster than Al can go back in (SSZ-33 study), even when we treat a material with boron in the lattice

Studies of Aluminum Reinsertion into Borosilicate Zeolites with Intersecting Channels of 10- and 12-Ring Channel Systems

The work here describes the kinetic analyses of aluminum replacement for boron in a suite of borosilicate molecular sieves. While the method has been described before as a means of converting synthesized borosilicates (with weak inherent acidity) to aluminosilicates (with much stronger acid strength) when there are large pores in the structure, here we carry out the transformation under less than optimal replacement concentrations, in order to better follow the kinetics. We examined several zeolite structures with boundary conditions of boron MEL where there are only 10-ring (or intermediate) pore structures and no Al is taken up, to multidimensional large pore zeolites, like boron beta, where Al substitution can occur everywhere. We also studied materials with both intermediate and large pores, SSZ-56, 57, 70, and 82. In the case of 57 up to 90% of the structure is made up of boron MEL. We observe that the pH drop is proportional to the Al reinsertion and is the same for all zeolites we studied. In one case, we compared a zeolite (SSZ-24) with boron and then no boron sites and found that Al does not go into defect sites. It was again confirmed (shown in earlier work) that Al will go into nest sites created by boron hydrolysis out of the substrate before Al treatment. Along those lines we also made two new observations: (1) the profile for Al uptake, as followed by pH drop, is the same kinetically, whether the boron is there or not; and (2) NMR showed that the boron is leaving the structure faster than Al can go back in (SSZ-33 study), even when we treat a material with boron in the lattice

Novel surfactant-free route to delaminated all-silica and titanosilicate zeolites derived from a layered borosilicate MWW precursor

Layered borosilicate zeolite precursor ERB-1P (Si/B = 11) is delaminated via simultaneous deboronation and SDA removal, to yield material DZ-1 consisting of silanol nests, using a simple aqueous Zn(NO_3)_2 treatment. Characterization of this synthesis process by PXRD shows loss of long-range order, and transmission electron microscopy (TEM) demonstrates transformation of rectilinear layers in the layered zeolite precursor to single and curved layers in the delaminated material. N_2 physisorption confirms the expected decrease of micropore volume and increase in external surface area for delaminated materials relative to their calcined 3D zeolite counterpart. Elemental analysis shows loss of B and absence of Zn in the delaminated material. Resonances corresponding to silanol nests are evident via^(29)Si solid-state NMR spectroscopy in DZ-1, which should be located within 12-MR pockets near the external surface. We have successfully utilized these nests as tetrahedral recognition sites for incorporation of Ti within an isolated framework coordination environment in material Ti-DZ-1. Diffuse-reflectance ultraviolet (DR-UV) spectroscopy of Ti-DZ-1 confirms isolated framework Ti sites, which are assigned to bands in the range of 210 nm–230 nm. Infrared spectra of Ti-DZ-1 consist of a distinct absorption band at 960 cm^(−1), which is absent in DZ-1 prior to Ti incorporation and has been previously correlated with the presence of framework Ti species. Infrared spectra after pyridine adsorption demonstrate bands consistent with Lewis-acid sites in the resulting Ti-substituted delaminated zeolite. The accessibility of these Lewis-acid sites is confirmed when using Ti-DZ-1 as a catalyst for cyclohexene epoxidation using tert-butyl hydroperoxide as the organic oxidant – a reaction for which both DZ-1 and TS-1 are inactive

Boron Sites in Borosilicate Zeolites at Various Stages of Hydration Studied by Solid State NMR Spectroscopy

The local structures of framework boron atoms in borosilicate zeolites B-β, B-SSZ-33 and B-SSZ-42 have been studied in the course of hydration/dehydration by employing solid-state NMR methods. In particular, characterization of trigonal boron sites has been studied in great detail. ^(11)B MAS NMR spectra showed that boron trigonally coordinated to the framework (B(OSi)_3, denoted as B[3]) can be readily transformed to a defective trigonal boron site (B(OSi)_2(OH), denoted as B[3]-I) as a result of hydration. The presence of B[3]-I sites was proven by utilizing a number of different NMR methods including ^(11)B MAS NMR at two different fields (11.7 and 19.6 T), ^(11)B MQMAS, ^(11)B CPMAS, and ^(11)B 2D HETCOR experiments. The B[3]-I species can be converted into B[3] upon dehydroxylation, but its presence can also be sustained even after very high-temperature treatment (at least up to 500 °C). The formation of deboronated species, B(OH)_3, in distorted form was detected even under a mild hydration treatment. HETCOR NMR revealed that hydroxyl protons with chemical shifts at 2.4 and 3.3 ppm in ^1H NMR are correlated with B[3] and B[3]-I sites, respectively. The presence of a new hydroxyl proton at 3.8 ppm in ^1H NMR that showed selective correlation with B[3]-I in HETCOR NMR was also identified

Role of Delamination in Zeolite-Catalyzed Aromatic Alkylation: UCB‑3 versus 3‑D Al-SSZ-70

Delaminated zeolite UCB-3 exhibits 2.4-fold greater catalytic activity relative to its three-dimensional (3D) zeolite counterpart, Al-SSZ-70, and 2.0-fold greater activity (per catalyst mass) when compared with industrial catalyst MCM-22, for the alkylation of toluene with propylene at 523 K. The former increase is nearly equal to the observed relative increase in external surface area and acid sites upon delamination. However, at 423 K for the same reaction, UCB-3 exhibits a 3.5-fold greater catalytic activity relative to 3D Al-SSZ-70. The higher relative rate enhancement for the delaminated material at lower temperature can be elucidated on the basis of increased contributions from internal acid sites. Evidence of possible contributions from such acid sites is obtained by performing catalysis after silanation treatment, which demonstrates that although virtually all catalysis in MCM-22 occurs on the external surface, catalysis also occurs on internal sites for 3D Al-SSZ-70. The additional observed enhancement at low temperatures can therefore be rationalized by greater access to internal active sites as a result of sheet breakage during delamination. Such breakage leads to shorter characteristic internal diffusion paths and was visualized using TEM comparisons of UCB-3 and 3D Al-SSZ-70