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The development of improved zeolite materials for applications in separation and catalysis requires understanding of mass transport. Herein, diffusion of single molecules is tracked in the straight and sinusoidal channels of the industrially relevant ZSM-5 zeolites using a combination of single-molecule localization microscopy and uniformly oriented zeolite thin films. Distinct motion behaviors are observed in zeolite channels with the same geometry, suggesting heterogeneous guest-host interactions. Quantification of the diffusion heterogeneities in the sinusoidal and straight channels suggests that the geometry of zeolite channels dictates the mobility and motion behavior of the guest molecules, resulting in diffusion anisotropy. The study of hierarchical zeolites shows that the addition of secondary pore networks primarily enhances the diffusivity of sinusoidal zeolite channels, and thus alleviating the diffusion limitations of microporous zeolites.

Establishing structure–reactivity relationships for specific channel orientations of zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, a well‐defined model system was developed to build structure–reactivity relationships for specific zeolite‐channel orientations during various catalytic reaction processes, for example, the methanol‐ and ethanol‐to‐hydrocarbons (MTH and ETH) process as well as oligomerization reactions. The entrapped and effluent hydrocarbons from single‐oriented zeolite ZSM‐5 channels during the MTH process were monitored by using operando UV/Vis diffuse reflectance spectroscopy (DRS) and on‐line mass spectrometry (MS), respectively. The results reveal that the straight channels favor the formation of internal coke, promoting the aromatic cycle. Furthermore, the sinusoidal channels produce aromatics, (e.g., toluene) that further grow into larger polyaromatics (e.g., graphitic coke) leading to deactivation of the zeolites. This underscores the importance of careful engineering of materials to suppress coke formation and tune product distribution by rational control of the location of zeolite acid sites and crystallographic orientations., A well‐defined model system was developed to establish structure–reactivity relationships for specific zeolite‐channel orientations during catalytic reactions, such as the methanol‐to‐hydrocarbons process. Straight zeolite‐channels favor the formation of internal coke, promoting the aromatic cycle, and sinusoidal zeolite‐channels produce aromatics that eventually grow into condensed polyaromatics at the surface leading to deactivation of the zeolites.

The development of improved zeolite materials for applications in separation and catalysis requires understanding of mass transport. Herein, diffusion of single molecules is tracked in the straight and sinusoidal channels of the industrially relevant ZSM-5 zeolites using a combination of single-molecule localization microscopy and uniformly oriented zeolite thin films. Distinct motion behaviors are observed in zeolite channels with the same geometry, suggesting heterogeneous guest-host interactions. Quantification of the diffusion heterogeneities in the sinusoidal and straight channels suggests that the geometry of zeolite channels dictates the mobility and motion behavior of the guest molecules, resulting in diffusion anisotropy. The study of hierarchical zeolites shows that the addition of secondary pore networks primarily enhances the diffusivity of sinusoidal zeolite channels, and thus alleviating the diffusion limitations of microporous zeolites.

Metal oxide-zeolite bifunctional catalysts allow coupling of reactions and so enhance catalytic processes, but structure and reactivity control is difficult. Here, a general synthesis is presented for metal oxide-zeolite double-shelled hollow spheres, which outperform other catalysts for petroleum production. Metal-zeolite composites with metal (oxide) and acid sites are promising catalysts for integrating multiple reactions in tandem to produce a wide variety of wanted products without separating or purifying the intermediates. However, the conventional design of such materials often leads to uncontrolled and non-ideal spatial distributions of the metal inside/on the zeolites, limiting their catalytic performance. Here we demonstrate a simple strategy for synthesizing double-shelled, contiguous metal oxide@zeolite hollow spheres (denoted as MO@ZEO DSHSs) with controllable structural parameters and chemical compositions. This involves the self-assembly of zeolite nanocrystals onto the surface of metal ion-containing carbon spheres followed by calcination and zeolite growth steps. The step-by-step formation mechanism of the material is revealed using mainly in situ Raman spectroscopy and X-ray diffraction and ex situ electron microscopy. We demonstrate that it is due to this structure that an Fe2O3@H-ZSM-5 DSHSs-showcase catalyst exhibits superior performance compared with various conventionally structured Fe2O3-H-ZSM-5 catalysts in gasoline production by the Fischer-Tropsch synthesis. This work is expected to advance the rational synthesis and research of hierarchically hollow, core-shell, multifunctional catalyst materials.

Zeolites and zeotype materials are heavily used in chemical industry as heterogeneous catalysts for the manufacturing of transportation fuels, chemicals and materials, such as polymers. This interest stimulates continuous research, both in academia and industry, to develop and apply new zeolite materials as well as improved catalytic, adsorption and separation technologies. Furthermore, there is vast interest to better understand the chemical and physical properties of zeolite-based materials. In this PhD Thesis, we have synthesized uniformly oriented, catalytically active zeolite thin-films and membranes as promising reaction and separation platforms. We have further demonstrated that these materials can also be used as viable model systems to study the intricate physicochemical changes taking place during catalytic processes. More specifically, in Chapters 2 and 3, uniformly oriented zeolite ZSM-5 thin-films (Chapter 2) and related membrane materials (Chapter 3) have been subsequently synthesized, characterized and tested. These systems were then used to study the deactivation behavior of zeolite ZSM-5 at the level of single oriented channels (Chapter 4) as well as at the nanometer scale (Chapter 6) during the methanol-to-hydrocarbons (MTH) process. Inspired by these works, well-oriented zeolite crystals were developed to study the effect of channel geometries on reaction behavior (Chapter 5) during the MTH process. Finally, the molecular diffusion patterns within single oriented zeolite channels (Chapter 7) were also investigated by using single molecule fluorescence microscopy.

Micropore topology and crystal size are two independently adjustable properties that govern the internal mass transport limitations of zeolite catalysts. Deciphering the relative impact of each factor on catalyst performance is often nontrivial owing to the inability to synthesize zeolites with predetermined physicochemical properties. In this study, a series of ZSM-11 (MEL) and ZSM-5 (MFI) catalysts of equivalent acidity, but differing pore architecture, are prepared with well-defined crystal sizes to elucidate the effects of diffusion path length versus topology on catalyst lifetime and selectivity. For these studies, we selected the methanol to hydrocarbons (MTH) reaction to assess the impact of design variables on the hydrocarbon pool (HCP) mechanism. Operando UV-vis microspectroscopy is used to investigate the evolution of active HCP species and heavier aromatic coking species during the transient start up period over both catalysts. Our findings reveal that slight variations in framework topology between MEL and MFI zeolites lead to marked differences in their catalytic performance as well as the evolutionary behavior of HCP species within the zeolite pores. We report that the diffusion limitations imposed by the tortuous channels in ZSM-5 catalysts are analogous to increasing the channel length in ZSM-11 catalysts via larger crystal sizes. Notably, we observe similar (albeit slightly offset) trends in MTH selectivity and HCP speciation for both zeolite framework types; however, differences in pore topology and catalyst size exact different effects on the evolution of intracrystalline hydrocarbon species. Collectively, these findings provide evidence that ZSM-11 is an effective medium-sized pore zeolite catalyst for reactions encumbered by rapid coking that often elicits premature deactivation.

Understanding the role of chemical dopants is crucial to modulating the optoelectronic properties of monolayer (ML) MoS2 and realizing its optoelectronic applications such as photodetectors, switching devices, and ultrathin transistors. Here, the effect of the dopant phase of the same dopants—liquid and gaseous—on the optical properties of ML MoS2 has been investigated using in situ Raman microspectroscopy with an environment-controlled reaction cell. The results show that the gaseous n-type dopant, that is, pyridine, completely quenched the PL intensity of ML MoS2, while liquid pyridine preserved 50% of the original PL intensity attributed to its less effective charge transfer to MoS2 than the gaseous counterpart. Photoemission of the quenched MoS2 could not be recovered with mild annealing in nitrogen and only partially recovered upon long-term exposure to air. The results show that the dopant phase strongly impacts the PL properties of ML MoS2.

International audience; Zeolite-based catalysts are globally employed in many industrial processes, such as in crude-oil refining and in the production of bulk chemicals. However, to be implemented in industrial reactors efficiently, zeolite powders are required to be shaped in catalyst bodies. Scale-up of zeolite catalysts into such forms comes with side effects to its overall physicochem-ical properties and to those of its constituting components. Although fundamental research into "technical" solid catalysts is scarce, binder effects have been reported to significantly impact their catalytic properties and lifetime. Given the large number of additional (in)organic components added in the formulation, it is somehow surprising to see that there is a distinct lack of research into the unintentional impact organic additives can have on the properties of the zeolite and the catalyst bodies in general. Here, we systematically prepared a series of alumina-bound zeolite ZSM-5-based catalyst bodies, with organic additives such as peptizing, plasticizing, and lubricating agents, to rationalize their impacts on the physicochemical properties of the shaped catalyst bodies. By utilizing a carefully selected arsenal of bulk and high-spatial resolution multiscale characterization techniques, as well as specifically sized bioinspired fluorescent nanoprobes to study pore accessibility, we clearly show that, although the organic additives achieve their primary function of a mechanically robust material, uncontrolled processes are taking place in parallel. We reveal that the extrusion process can lead to zeolite dealumination (from acid peptizing treatment, and localized steaming upon calcination); meso-and macropore structural rearrangement (via burning-out of organic plasticizing and lubricating agents upon calcination); and abating of known alumina binder effects (via scavenging of Al species via chelating lubricating agents), which significantly impact catalytic performance. Understanding the mechanisms behind such effects in industrial-grade catalyst formulations can lead to enhanced design of these important materials, which can improve process efficiency in a vast range of industrial catalytic reactions.

Although industrialized, the mechanism for catalytic upgrading of bioethanol over solid-acid catalysts (that is, the ethanol-to-hydrocarbons (ETH) reaction) has not yet been fully resolved. Moreover, mechanistic understanding of the ETH reaction relies heavily on its well-known “sister-reaction” the methanol-to-hydrocarbons (MTH) process. However, the MTH process possesses a C 1 -entity reactant and cannot, therefore, shed any light on the homologation reaction sequence. The reaction and deactivation mechanism of the zeolite H-ZSM-5-catalyzed ETH process was elucidated using a combination of complementary solid-state NMR and operando UV/Vis diffuse reflectance spectroscopy, coupled with on-line mass spectrometry. This approach establishes the existence of a homologation reaction sequence through analysis of the pattern of the identified reactive and deactivated species. Furthermore, and in contrast to the MTH process, the deficiency of any olefinic-hydrocarbon pool species (that is, the olefin cycle) during the ETH process is also noted.

Monolayer (ML) MoS2 has become a very promising two-dimensional material for photorelated applications, potentially serving as the basis for an ultrathin photodetector, switching device, or transistors because of its strong interaction with light in ambient conditions. Establishing the impact of individual ambient gas components on the optical properties of MoS2 is a necessary step toward application development. By using in situ Raman microspectroscopy with an environment-controlled reaction cell, the photoluminescence (PL) intensity of chemical vapor deposition (CVD)-grown MoS2 MLs is monitored at different intralayer locations under ambient and controlled gas environments, such as N2, O2, and H2O. This new approach enables us to monitor the optical properties of MoS2 at different locations on the flakes and separate the role of photoreaction of various gases during laser irradiation. Upon mild photoirradiation in ambient conditions, the PL intensity in the interior of the ML MoS2 flakes remains unchanged, while the PL intensity at the edge region increases drastically. Photoirradiation in controlled gas environments reveals that O2 is necessary to increase the PL intensity at the MoS2 flake edges, attributed to the charge transfer of chemisorbed O2. N2 or H2O and N2 environments induce decreasing PL intensity upon repetitive laser irradiation. However, the H2O and O2 gas mixture, a combination designed to mimic ambient conditions, is necessary to maintain the PL intensity at the interior of the ML MoS2 flakes. Our study demonstrates that photoreactions with the gaseous environment on the MoS2 ML flakes should be taken into consideration even upon mild photoirradiation because they strongly impact the flakes’ optical properties.

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.

Understanding the 3-D distribution and nature of active sites in heterogeneous catalysts is critical to developing structure-function relationships. However, this is difficult to achieve in microporous materials as there is little relative z-contrast between active and inactive framework elements (e.g., Al, O, P, and Si), making them difficult to differentiate with electron microscopies. We have applied atom probe tomography (APT), currently the only nanometer-scale 3-D microscopy to offer routine light element contrast, to the methanol-to-hydrocarbons (MTH) catalyst SAPO-34, with Si as the active site, which may be present in the framework as either isolated Si species or clusters (islands) of Si atoms. 29Si solid-state NMR data on isotopically enriched and natural abundance materials are consistent with the presence of Si islands, and the APT results have been complemented with simulations to show the smallest detectable cluster size as a function of instrument spatial resolution and detector efficiency. We have identified significant Si-Si affinity in the materials, as well as clustering of coke deposited by the MTH reaction (13CH3OH used) and an affinity between Brønsted acid sites and coke. A comparison with simulations shows that the ultimate spatial resolution that can be attained by APT applied to molecular sieves is 0.5-1 nm. Finally, the observed 13C clusters are consistent with hydrocarbon pool mechanism intermediates that are preferentially located in regions of increased Brønsted acidity.

Large crystals of zeolite ferrierite (FER) are important model systems for spatially resolved catalysis and diffusion studies, though there is considerable variation in crystal habit depending on the chemical composition and employed synthesis conditions. A synergistic combination of techniques has been applied, including single crystal X‐ray diffraction, high‐temperature in situ confocal fluorescence microscopy, fluorescent probe molecules, wide‐field microscopy and atomic force microscopy to unravel the internal architecture of three distinct FER zeolites. Pyrolyzed template species can be used as markers for the 8‐membered ring direction as they are trapped in the terraced roof of the FER crystals. This happens as the materials grow in a layer‐by‐layer, defect‐free manner normal to the large crystal surface, and leads to a facile method to diagnose the pore system orientation, which avoids tedious single crystal X‐ray diffraction experiments.

Monolayer (ML) MoS2 has become a very promising two-dimensional material for photorelated applications, potentially serving as the basis for an ultrathin photodetector, switching device, or transistors because of its strong interaction with light in ambient conditions. Establishing the impact of individual ambient gas components on the optical properties of MoS2 is a necessary step toward application development. By using in situ Raman microspectroscopy with an environment-controlled reaction cell, the photoluminescence (PL) intensity of chemical vapor deposition (CVD)-grown MoS2 MLs is monitored at different intralayer locations under ambient and controlled gas environments, such as N2, O2, and H2O. This new approach enables us to monitor the optical properties of MoS2 at different locations on the flakes and separate the role of photoreaction of various gases during laser irradiation. Upon mild photoirradiation in ambient conditions, the PL intensity in the interior of the ML MoS2 flakes remains unchanged, while the PL intensity at the edge region increases drastically. Photoirradiation in controlled gas environments reveals that O2 is necessary to increase the PL intensity at the MoS2 flake edges, attributed to the charge transfer of chemisorbed O2. N2 or H2O and N2 environments induce decreasing PL intensity upon repetitive laser irradiation. However, the H2O and O2 gas mixture, a combination designed to mimic ambient conditions, is necessary to maintain the PL intensity at the interior of the ML MoS2 flakes. Our study demonstrates that photoreactions with the gaseous environment on the MoS2 ML flakes should be taken into consideration even upon mild photoirradiation because they strongly impact the flakes’ optical properties.

A state-of-the-art review of the behavior of interfaces between granular materials and solid structural components is presented. The review includes both the experimental and theoretical researches on the interfaces between soils and steel, as well as those between soils and concrete. Development of constitutive relations of such interfaces is also summarized. Furthermore, numerical techniques, both the Finite Element Method and the Discrete Element Method (DEM), to simulate the interface behaviors are stated. Aspects for future development in this area are also included.

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.