Min Bum Park

Synthesis and Characterization of ERI-Type UZM-12 Zeolites and Their Methanol-to-Olefin Performance

A wide variety of different linear, diquaternary alkylammonium ions have been used as supplementary crystallization structure-directing agents (SDAs) in the synthesis of UZM-12, a high-silica version of zeolite erionite, via a charge density mismatch (CDM) approach. When tetraethylammonium is used as a CDM SDA, the crystallization of UZM-12 was found to be critically dependent not only on the type of alkali metal cations added as another crystallization SDA to the synthesis mixture, but also on the size of the groups on the diquaternary ammonium ion employed and the length of its central polymethylene chain that are closely related to the dimensions of cylindrical 23-hedral [4(12)6(5)8(6)] eri cages in this small-pore zeolite. (27)Al MQ MAS NMR measurements reveal a preferential location of Al on the high-multiplicity site over the lower-multiplicity site of the UZM-12 framework. The catalytic results from the methanol-to-olefin reaction over a series of H-UZM-12 zeolites with similar acidic properties but different crystallite sizes (100-2500 nm in length) demonstrate that the nanocrystallinity (probably the ≤100 nm range) may have a detrimental effect on the activity and stability for this reaction, probably due to the fast buildup of large coke molecules on the external surface of zeolite crystallites that inhibits the methanol diffusion to intrazeolitic acid sites, rendering them ultimately inaccessible for catalysis.

Formation Pathway for LTA Zeolite Crystals Synthesized via a Charge Density Mismatch Approach

A solid understanding of the molecular-level mechanisms responsible for zeolite crystallization remains one of the most challenging issues in modern zeolite science. Here we investigated the formation pathway for high-silica LTA zeolite crystals in the simultaneous presence of tetraethylammonium (TEA(+)), tetramethylammonium (TMA(+)), and Na(+) ions as structure-directing agents (SDAs) with the goal of better understanding the charge density mismatch synthesis approach, which was designed to foster cooperation between two or more different SDAs. Nucleation was found to begin with the formation of lta-cages rather than the notably smaller sod and d4r-cages, with concomitant incorporation of TMA(+) and Na(+) into a very small amount of the solid phase with a low Si/Al ratio (ca. 2.5). The overall characterization results of our work demonstrate that sod-cages are first built around the preorganized lta-cages and that d4r-cages are in turn constructed by the progressive addition of low-molecular-weight (alumino)silicate species, which promotes the formation and growth of embryonic LTA zeolite crystals. We also show that the crystal growth may take place by a similar process in which TEA(+) is also incorporated, forming a single LTA zeolite phase with a higher Si/Al ratio (ca. 3.3).

Synthesis of Aluminosilicate and Gallosilicate Zeolites via a Charge Density Mismatch Approach and Their Characterization

Aluminosilicate and gallosilicate zeolite syntheses via a charge density mismatch (CDM) approach are compared at intermediate-silica compositions (Si/Me = 5-16, where Me is Al or Ga). With a variation of the crystallization temperature and of the type and/or concentration of alkali metal ions added as a crystallization structure-directing agent (SDA) to tetraethylammonium-tetramethylammonium, tetraethylammonium-hexamethonium, and strontium-choline mixed-SDA systems, we were able to obtain 11 different zeolite structures. However, only 5 out of a total 40 pairs of aluminosilicate and gallosilicate synthesis runs at otherwise identical chemical compositions were found to give the same zeolite product with no detectable impurities, suggesting that the structure-directing ability of Ga is quite different from that of Al even in intermediate-silica synthesis conditions. The CDM approach to offretite synthesis led to hexagonal plate-like crystals with aspect ratios lower than 0.3, and UZM-22 exhibited no significant preference of Al substitution for particular tetrahedral sites, especially for site T1, unlike its framework type material ZSM-18. More interestingly, the EU-1 zeolite obtained from an aluminosilicate synthesis mixture containing Li(+) as an inorganic crystallization SDA in the tetraethylammonium-hexamethonium double-organic additive system has been characterized to locate about half of its Li(+) ions in the framework, while the Li distribution over the 10 topologically different tetrahedral sites is nonrandom in nature.

In-situ dehydration studies of fully K-, Rb-, and Cs-exchanged natrolites

Abstract In-situ synchrotron X-ray powder diffraction studies of K-, Rb-, and Cs-exchanged natrolites between room temperature and 425 °C revealed that the dehydrated phases with collapsed frameworks start to form at 175, 150, and 100°C, respectively. The degree of the framework collapse indicated by the unit-cell volume contraction depends on the size of the non-framework cation: K-exchanged natrolite undergoes an 18.8% unit-cell volume contraction when dehydrated at 175 °C, whereas Rband Cs-exchanged natrolites show unit-cell volume contractions of 18.5 and 15.2% at 150 and 100°C, respectively. In the hydrated phases, the dehydration-induced unit-cell volume reduction diminishes as the cation size increases and reveals increasingly a negative slope as smaller cations are substituted into the pores of the natrolite structure. The thermal expansion of the unit-cell volumes of the dehydrated K-, Rb-, and Cs-phases have positive thermal expansion coefficients of 8.80 × 10−5 K−1, 1.03 × 10−4 K−1, and 5.06 × 10−5 K−1, respectively. Rietveld structure refinements of the dehydrated phases at 400 °C reveal that the framework collapses are due to an increase of the chain rotation angles, ψ, which narrow the channels to a more elliptical shape. Compared to their respective hydrated structures at ambient conditions, the dehydrated K-exchanged natrolite at 400°C shows a 2.2-fold increase in ψ, whereas the dehydrated Rb- and Cs-natrolites at 400°C reveal increases of ψ by ca. 3.7 and 7.3 times, respectively. The elliptical channel openings of the dehydrated K-, Rb-, to Cs-phases become larger as the cation size increases. The disordered non-framework cations in the hydrated K-, Rb-, and Csnatrolite order during dehydration and the subsequent framework collapse. The dehydrated phases of Rb- and Cs-natrolite can be stabilized at ambient conditions

A Family of Molecular Sieves Containing Framework‐Bound Organic Structure‐Directing Agents

Organic structure-directing agents (OSDAs), such as quaternary ammonium cations and amines, used in the synthesis of zeolites and related crystalline microporous oxides usually end up entrapped inside the void spaces of the crystallized inorganic host lattice. But none of them is known to form direct chemical bonds to the framework of these industrially important catalysts and adsorbents. We demonstrate that ECR-40, currently regarded as a typical silicoaluminophosphate molecular sieve, constitutes instead a new family of inorganic-organic hybrid networks in which the OSDAs are covalently bonded to the inorganic framework. ECR-40 crystallization begins with the formation of an Al-OSDA complex in the liquid phase in which the Al is octahedrally coordinated. This unit is incorporated in the crystallizing ECR-40. Subsequent removal of framework-bound OSDAs generates Al-O-Al linkages in a fully tetrahedrally coordinated framework.