Factors controlling the molecular modification of one-dimensional zeolites.

Interactions between organic molecules and inorganic materials are ubiquitous in many applications and often play significant roles in directing pathways of crystallization. It is frequently debated whether kinetics or thermodynamics plays a more prominent role in the ability of molecular modifiers to impact crystal nucleation and growth processes. In the case of nanoporous zeolites, approaches in rational design often capitalize on the ability of organics, used as either modifiers or structure-directing agents, to markedly impact the physicochemical properties of zeolites. It has been demonstrated for multiple topologies that modifier-zeolite interactions can alter crystal size and morphology, yet few studies have distinguished the roles of thermodynamics and kinetics. We use a combination of calorimetry and molecular modeling to estimate the binding energies of organics on zeolite surfaces and correlate these results with synthetic trends in crystal morphology. Our findings reveal unexpectedly small energies of interaction for a range of modifiers with two zeolite structures, indicating the effect of organics on zeolite crystal surface free energy is minor and kinetic factors most likely govern growth modification.

Crystallization of Mordenite Platelets using Cooperative Organic Structure-Directing Agents.

Organic structure-directing agents (OSDAs) are exploited in the crystallization of microporous materials to tailor the physicochemical properties of the resulting zeolite for applications ranging from separations to catalysis. The rational design of these OSDAs often entails the identification of molecules with a geometry that is commensurate with the channels and cages of the target zeolite structure. Syntheses tend to employ only a single OSDA, but there are a few examples where two or more organics operate synergistically to yield a desired product. Using a combination of state-of-the-art characterization techniques and molecular modeling, we show that the coupling of N,N,N-trimethyl-1,1-adamantammonium and 1,2-hexanediol, each yielding distinct zeolites when used alone, results in the cooperative direction of a third structure, HOU-4, with the mordenite framework type (MOR). Rietveld refinement using synchrotron X-ray diffraction data reveals the spatial arrangement of the organics in the HOU-4 crystals, with amines located in the large channels and alcohols oriented in the side pockets lining the one-dimensional pores. These results are in excellent agreement with molecular dynamics calculations, which predict similar spatial distributions of organics with an energetically favorable packing density that agrees with experimental measurements of OSDA loading, as well as with solid-state two-dimensional 27Al{29Si}, 27Al{1H}, and 13C{1H} NMR correlation spectra, which establish the proximities and interactions of occluded OSDAs. A combination of high-resolution transmission electron microscopy and atomic force microscopy is used to quantify the size of the HOU-4 crystals, which exhibit a platelike morphology, and to index the crystal facets. Our findings reveal that the combined OSDAs work in tandem to produce ultrathin, nonfaulted HOU-4 crystals that exhibit improved catalytic activity for cumene cracking in comparison to mordenite crystals prepared via conventional syntheses. This novel demonstration of cooperativity highlights the potential possibilities for expanding the use of dual structure-directing agents in zeolite synthesis.

Structuring of Organic Solvents at Solid Interfaces and Ramifications for Antimalarial Adsorption on ß-Hematin Crystals.

A critical aspect of material synthesis is solvent structuring at solid-liquid interfaces, which can impact the adsorption of solute and growth modifiers on an underlying substrate. In general, the impact of solvent structuring on molecular sorbate interactions with solid sorbents is poorly understood. This is particularly true for processes that occur in organic media, such as hematin crystallization, which is crucial to the survival of malaria parasites. Here, we use chemical force microscopy and molecular modeling to analyze the interactions between functional moieties of known antimalarials and the interface between ß-hematin crystals and a mixed organic (octanol)-aqueous solvent. We show that the ß-hematin surface, patterned in parallel hydrophobic and hydrophilic stripes, engenders the assembly of up to five layers of octanol molecules aligned parallel to the crystal surface. In contrast, studies of solvent structuring on a disordered glass surface reveal that octanol molecules align perpendicular to the interface. The distinct octanol arrays direct molecule adsorption at the respective interfaces. At both substrates, we also find stabilized pockets of aqueous nanophase lining the surfaces. A combination of experimental analyses and modeling of solvent structuring provides crucial insights into the association of hematin molecules with growing crystals as well as the adsorption and mobility of antimalarial drugs. Moreover, our findings offer a general perspective on the collective behaviors of complex organic solvents that may apply to a broad range of interactions at solid-liquid interfaces.