Joel E. Schmidt

Synthesis of a Specified, Silica Molecular Sieve by Using Computationally Predicted Organic Structure-Directing Agents†

Crystalline molecular sieves are used in numerous applications, where the properties exploited for each technology are the direct consequence of structural features. New materials are typically discovered by trial and error, and in many cases, organic structure-directing agents (OSDAs) are used to direct their formation. Here, we report the first successful synthesis of a specified molecular sieve through the use of an OSDA that was predicted from a recently developed computational method that constructs chemically synthesizable OSDAs. Pentamethylimidazolium is computationally predicted to have the largest stabilization energy in the STW framework, and is experimentally shown to strongly direct the synthesis of pure-silica STW. Other OSDAs with lower stabilization energies did not form STW. The general method demonstrated here to create STW may lead to new, simpler OSDAs for existing frameworks and provide a way to predict OSDAs for desired, theoretical frameworks.

Enantiomerically enriched, polycrystalline molecular sieves

Significance Zeolites and zeolite-like molecular sieves are used as adsorbents and heterogeneous catalysts to prepare a wide variety of products ranging from gasoline to monomers for polymers such as polyethylene terephthalate, which is used in plastic bottles. Pharmaceuticals, pesticides, fragrances, and components in food can contain chiral centers. Here, we prepare enantioenriched polycrystalline samples of a molecular sieve and show that this type of porous material can function as an adsorbent to separate chiral molecules and as a heterogeneous catalyst to perform chiral reactions. This initial demonstration proves that bulk, enantioenriched chiral zeolites and zeolite-like molecular sieves can be synthesized and that this type of solid can be used to prepare chiral, small molecules. Zeolite and zeolite-like molecular sieves are being used in a large number of applications such as adsorption and catalysis. Achievement of the long-standing goal of creating a chiral, polycrystalline molecular sieve with bulk enantioenrichment would enable these materials to perform enantioselective functions. Here, we report the synthesis of enantiomerically enriched samples of a molecular sieve. Enantiopure organic structure directing agents are designed with the assistance of computational methods and used to synthesize enantioenriched, polycrystalline molecular sieve samples of either enantiomer. Computational results correctly predicted which enantiomer is obtained, and enantiomeric enrichment is proven by high-resolution transmission electron microscopy. The enantioenriched and racemic samples of the molecular sieves are tested as adsorbents and heterogeneous catalysts. The enantioenriched molecular sieves show enantioselectivity for the ring opening reaction of epoxides and enantioselective adsorption of 2-butanol (the R enantiomer of the molecular sieve shows opposite and approximately equal enantioselectivity compared with the S enantiomer of the molecular sieve, whereas the racemic sample of the molecular sieve shows no enantioselectivity).

Coke Formation in a Zeolite Crystal During the Methanol-to- Hydrocarbons Reaction as Studied with Atom Probe Tomography

Abstract Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub‐nm length scale in a single zeolite ZSM‐5 crystal, which has been partially deactivated by the methanol‐to‐hydrocarbons reaction using 13C‐labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30–60 13C atoms. These clusters correlate with local increases in Brønsted acid site density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. This nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.

Template-Framework Interactions in Tetraethylammonium-Directed Zeolite Synthesis.

Abstract Zeolites, having widespread applications in chemical industries, are often synthesized using organic templates. These can be cost‐prohibitive, motivating investigations into their role in promoting crystallization. Herein, the relationship between framework structure, chemical composition, synthesis conditions and the conformation of the occluded, economical template tetraethylammonium (TEA+) has been systematically examined by experimental and computational means. The results show two distinct regimes of occluded conformer tendencies: 1) In frameworks with a large stabilization energy difference, only a single conformer was found (BEA, LTA and MFI). 2) In the frameworks with small stabilization energy differences (AEI, AFI, CHA and MOR), less than the interconversion of TEA+ in solution, a heteroatom‐dependent (Al, B, Co, Mn, Ti, Zn) distribution of conformers was observed. These findings demonstrate that host–guest chemistry principles, including electrostatic interactions and coordination chemistry, are as important as ideal pore‐filling.

High-silica, heulandite-type zeolites prepared by direct synthesis and topotactic condensation

There are both natural minerals and synthetic zeolites that possess the HEU framework topology. These materials have a limited compositional range (Si/Al < 6), and the natural zeolites often contain a large amount of impurities such as Fe3+. The preparation of impurity-free HEU-type zeolites with higher Si/Al ratio could open many areas of application, particularly in catalysis. Here, we report the first high-silica HEU-type zeolite that can be prepared via two different procedures. In the first method high-silica HEU (denoted CIT-8) is prepared using a topotactic condensation mechanism (layered precursor denoted CIT-8P); CIT-8P is obtained from a low-water synthesis in fluoride media. CIT-8 prepared in this manner has a product Si/Al ratio of 9.8 ± 0.7 and a micropore volume of 0.10 cm3 g−1 (measured by nitrogen adsorption). The variable temperature powder X-ray diffraction shows that CIT-8 forms via topotactic condensation from CIT-8P along the b axis. Additionally, high-silica heulandite can be synthesized directly from a hydroxide-mediated reaction mixture (denoted CIT-8H), and has a Si/Al ratio of 6.4 ± 0.3 and a micropore volume of 0.10 cm3 g−1. Both synthesis methods produce zeolites that expand the compositional range of HEU-type zeolites. These synthetic methods allow for the addition of other heteroatoms, and titanium-containing CIT-8 is prepared as an illustrative example.

Computationally-Guided Synthesis of the 8-Ring Zeolite AEI

A computational method capable of predicting chemically-synthesizable organic structure directing agents (OSDAs) for targeted microporous material frameworks has been applied to the zeolite SSZ-39 (AEI framework topology). The top predicted OSDA has been found to have a more favorable stabilization energy than any of the OSDAs previously reported to form SSZ-39. This result was verified experimentally, demonstrating that this computational method is capable of predicting successful OSDAs for zeolite synthesis mixtures containing a large number of inorganic variables such as heteroatoms, inorganic cations, hydroxide media and high water content. This is a significant improvement over the first experimental validation of this computational method.

Facile Synthesis, Characterization, and Catalytic Behavior of a Large‐Pore Zeolite with the IWV Framework

Large-pore microporous materials are of great interest to process bulky hydrocarbon and biomass-derived molecules. ITQ-27 (IWV) has a two-dimensional pore system bounded by 12-membered rings (MRs) that lead to internal cross-sections containing 14 MRs. Investigations into the catalytic behavior of aluminosilicate (zeolite) materials with this framework structure have been limited until now due to barriers in synthesis. The facile synthesis of aluminosilicate IWV in both hydroxide and fluoride media is reported herein using simple, diquaternary organic structure-directing agents (OSDAs) that are based on tetramethylimidazole. In hydroxide media, a zeolite product with Si/Al=14.8-23.2 is obtained, while in fluoride media an aluminosilicate product with Si/Al up to 82 is synthesized. The material produced in hydroxide media is tested for the hydroisomerization of n-hexane, and results from this test reaction suggest that the effective pore size of zeolites with the IWV framework structure is similar to but slightly larger than that of ZSM-12 (MTW), in fairly good agreement with crystallographic data.

Structural and kinetic changes to small-pore Cu-zeolites after hydrothermal aging treatments and selective catalytic reduction of NOx with ammonia

Three small-pore, eight-membered ring (8-MR) zeolites of different cage-based topology (CHA, AEI, RTH), in their proton- and copper-exchanged forms, were first exposed to high temperature hydrothermal aging treatments (1073 K, 16 h, 10% (v/v) H2O) and then to reaction conditions for low temperature (473 K) standard selective catalytic reduction (SCR) of NOx with ammonia, in order to study the effect of zeolite topology on the structural and kinetic changes that occur to Cu-zeolites used in NOx abatement. UV-visible spectra were collected to monitor changes to Cu structure and showed that band intensities for isolated, hydrated Cu2+ cations (∼12 500 cm−1) remain constant after hydrothermal aging, but decrease in intensity upon subsequent exposure to low temperature SCR reaction conditions. Standard SCR rates (per Cu, 473 K), activation energies, and reaction orders are similar between Cu-AEI and Cu-CHA zeolites before and after hydrothermal aging, although rates are lower after hydrothermal aging as expected from the decreases in intensity of UV-visible bands for Cu2+ active sites. For Cu-RTH, rates are lower (by 2–3×) and apparent activation energies are lower (by ∼2×) than for Cu-AEI or Cu-CHA. These findings suggest that the RTH framework imposes internal transport restrictions, effectively functioning as a one-dimensional framework during SCR catalysis. Hydrothermal aging of Cu-RTH results in complete deactivation and undetectable SCR rates, despite X-ray diffraction patterns and Ar micropore volumes (87 K) that remain unchanged after hydrothermal aging treatments and subsequent SCR exposure. These findings highlight some of the differences in low temperature SCR behavior among small-pore Cu-zeolites of different topology, and the beneficial properties conferred by double six-membered ring (D6R) composite building units. They demonstrate that deleterious structural changes to Cu sites occur after exposure to hydrothermal aging conditions and SCR reactants at low temperatures, likely reflecting the formation of inactive copper-aluminate domains. Therefore, the viability of Cu-zeolites for practical low temperature NOx SCR catalysis cannot be inferred solely from assessments of framework structural integrity after hydrothermal aging treatments, but also require Cu active site and kinetic characterization after hydrothermally aged zeolites are exposed to low temperature SCR reaction conditions.

Nanoscale tomography reveals the deactivation of automotive copper-exchanged zeolite catalysts

Copper-exchanged zeolite chabazite (Cu-SSZ-13) was recently commercialized for the selective catalytic reduction of NOX with ammonia in vehicle emissions as it exhibits superior reaction performance and stability compared to all other catalysts, notably Cu-ZSM-5. Herein, the 3D distributions of Cu as well as framework elements (Al, O, Si) in both fresh and aged Cu-SSZ-13 and Cu-ZSM-5 are determined with nanometer resolution using atom probe tomography (APT), and correlated with catalytic activity and other characterizations. Both fresh catalysts contain a heterogeneous Cu distribution, which is only identified due to the single atom sensitivity of APT. After the industry standard 135,000 mile simulation, Cu-SSZ-13 shows Cu and Al clustering, whereas Cu-ZSM-5 is characterized by severe Cu and Al aggregation into a copper aluminate phase (CuAl2O4 spinel). The application of APT as a sensitive and local characterization method provides identification of nanometer scale heterogeneities that lead to catalytic activity and material deactivation.Cu-exchanged zeolite chabazite has superior stability over other catalysts in automotive NOx reduction. Here, the authors use atom probe tomography to create 3D nanoscale reconstructions of two Cu-containing zeolite catalysts, providing a complete picture of their deactivation mechanisms during aging.

Probing Zeolite Crystal Architecture and Structural Imperfections using Differently Sized Fluorescent Organic Probe Molecules

Abstract A micro‐spectroscopic method has been developed to probe the accessibility of zeolite crystals using a series of fluorescent 4‐(4‐diethylaminostyryl)‐1‐methylpyridinium iodide (DAMPI) probes of increasing molecular size. Staining large zeolite crystals with MFI (ZSM‐5) topology and subsequent mapping of the resulting fluorescence using confocal fluorescence microscopy reveal differences in structural integrity: the 90° intergrowth sections of MFI crystals are prone to develop structural imperfections, which act as entrance routes for the probes into the zeolite crystal. Polarization‐dependent measurements provide evidence for the probe molecules alignment within the MFI zeolite pore system. The developed method was extended to BEA (Beta) crystals, showing that the previously observed hourglass pattern is a general feature of BEA crystals with this morphology. Furthermore, the probes can accurately identify at which crystal faces of BEA straight or sinusoidal pores open to the surface. The results show this method can spatially resolve the architecture‐dependent internal pore structure of microporous materials, which is difficult to assess using other characterization techniques such as X‐ray diffraction.