Single-particle spectroscopy on large SAPO-34 crystals at work: methanol-to-olefin versus ethanol-to-olefin processes.

The formation of hydrocarbon pool (HCP) species during methanol-to-olefin (MTO) and ethanol-to-olefin (ETO) processes have been studied on individual micron-sized SAPO-34 crystals with a combination of in situ UV/Vis, confocal fluorescence, and synchrotron-based IR microspectroscopic techniques. With in situ UV/Vis microspectroscopy, the intensity changes of the λ=400 nm absorption band, ascribed to polyalkylated benzene (PAB) carbocations, have been monitored and fitted with a first-order kinetics at low reaction temperatures. The calculated activation energy (Ea ) for MTO, approximately 98 kJ mol(-1) , shows a strong correlation with the theoretical values for the methylation of aromatics. This provides evidence that methylation reactions are the rate-determining steps for the formation of PAB. In contrast for ETO, the Ea value is approximately 60 kJ mol(-1) , which is comparable to the Ea values for the condensation of light olefins into aromatics. Confocal fluorescence microscopy demonstrates that during MTO the formation of the initial HCP species are concentrated in the outer rim of the SAPO-34 crystal when the reaction temperature is at 600 K or lower, whereas larger HCP species are gradually formed inwards the crystal at higher temperatures. In the case of ETO, the observed egg-white distribution of HCP at 509 K suggests that the ETO process is kinetically controlled, whereas the square-shaped HCP distribution at 650 K is indicative of a diffusion-controlled process. Finally, synchrotron-based IR microspectroscopy revealed a higher degree of alkylation for aromatics for MTO as compared to ETO, whereas high reaction temperatures favor dealkylation processes for both the MTO and ETO processes.

Coke formation during the methanol-to-olefin conversion: in situ microspectroscopy on individual H-ZSM-5 crystals with different Brønsted acidity.

Coke formation during the methanol-to-olefin (MTO) conversion has been studied at the single-particle level with in situ UV/Vis and confocal fluorescence microscopy. For this purpose, large H-ZSM-5 crystals differing in their Si/Al molar ratio have been investigated. During MTO, performed at 623 and 773 K, three major UV/Vis bands assigned to different carbonaceous deposits and their precursors are observed. The absorption at 420 nm, assigned to methyl-substituted aromatic compounds, initiates the buildup of the optically active coke species. With time-on-stream, these carbonaceous compounds expand in size, resulting in the gradual development of a second absorption band at around 500 nm. An additional broad absorption band in the 600 nm region indicates the enhanced formation of extended carbonaceous compounds that form as the reaction temperature is raised. Overall, the rate of coke formation decreases with decreasing aluminum content. Analysis of the reaction kinetics indicates that an increased Brønsted acid site density facilitates the formation of larger coke species and enhances their formation rate. The use of multiple excitation wavelengths in confocal fluorescence microscopy enables the localization of coke compounds with different molecular dimensions in an individual H-ZSM-5 crystal. It demonstrates that small coke species evenly spread throughout the entire H-ZSM-5 crystal, whereas extended coke deposits primarily form near the crystal edges and surfaces. Polarization-dependent UV/Vis spectroscopy measurements illustrate that extended coke species are predominantly formed in the straight channels of H-ZSM-5. In addition, at higher temperatures, fast deactivation leads to the formation of large aromatic compounds within channel intersections and at the external zeolite surface, where the lack of spatial restrictions allows the formation of graphite-like coke.

Morphology-dependent zeolite intergrowth structures leading to distinct internal and outer-surface molecular diffusion barriers.

Zeolites play a crucial part in acid-base heterogeneous catalysis. Fundamental insight into their internal architecture is of great importance for understanding their structure-function relationships. Here, we report on a new approach correlating confocal fluorescence microscopy with focused ion beam-electron backscatter diffraction, transmission electron microscopy lamelling and diffraction, atomic force microscopy and X-ray photoelectron spectroscopy to study a wide range of coffin-shaped MFI-type zeolite crystals differing in their morphology and chemical composition. This powerful combination demonstrates a unified view on the morphology-dependent MFI-type intergrowth structures and provides evidence for the presence and nature of internal and outer-surface barriers for molecular diffusion. It has been found that internal-surface barriers originate not only from a 90 degrees mismatch in structure and pore alignment but also from small angle differences of 0.5 degrees-2 degrees for particular crystal morphologies. Furthermore, outer-surface barriers seem to be composed of a silicalite outer crust with a thickness varying from 10 to 200 nm.

Space- and time-resolved in-situ spectroscopy on the coke formation in molecular sieves: methanol-to-olefin conversion over H-ZSM-5 and H-SAPO-34.

Formation of coke in large H-ZSM-5 and H-SAPO-34 crystals during the methanol-to-olefin (MTO) reaction has been studied in a space- and time-resolved manner. This has been made possible by applying a high-temperature in-situ cell in combination with micro-spectroscopic techniques. The buildup of optically active carbonaceous species allows detection with UV/Vis microscopy, while a confocal fluorescence microscope in an upright configuration visualises the formation of coke molecules and their precursors inside the catalyst grains. In H-ZSM-5, coke is initially formed at the triangular crystal edges, in which straight channel openings reach directly the external crystal surface. At reaction temperatures ranging from 530 to 745 K, two absorption bands at around 415 and 550 nm were detected due to coke or its precursors. Confocal fluorescence microscopy reveals fluorescent carbonaceous species that initially form in the near-surface area and gradually diffuse inwards the crystal in which internal intergrowth boundaries hinder a facile penetration for the more bulky aromatic compounds. In the case of H-SAPO-34 crystals, an absorption band at around 400 nm arises during the reaction. This band grows in intensity with time and then decreases if the reaction is carried out between 530 and 575 K, whereas at higher temperatures its intensity remains steady with time on stream. Formation of the fluorescent species during the course of the reaction is limited to the near-surface region of the H-SAPO-34 crystals, thereby creating diffusion limitations for the coke front moving towards the middle of the crystal during the MTO reaction. The two applied micro-spectroscopic techniques introduced allow us to distinguish between graphite-like coke deposited on the external crystal surface and aromatic species formed inside the zeolite channels. The use of the methods can be extended to a wide variety of catalytic reactions and materials in which carbonaceous deposits are formed.

Unusual coordination behavior of Cr3+ in microporous aluminophosphates.

A CrAPO-5 molecular sieve has been investigated with X-ray absorption spectroscopy (EXAFS-XANES) as dehydrated material and after loading with water and ammonia to unravel the coordination geometries of Cr3+ in the framework of a microporous crystalline aluminophosphate, more particularly of the AFI-type. A comparison of the XANES data, a preedge analysis with crystal field multiplet calculations and EXAFS data, pointed toward the presence of framework Cr3+ which, on dehydration, takes on a distorted tetrahedral coordination state. Due to the 3d3 configuration of Cr3+, this unusual tetrahedral coordination environment strongly tends to transform into the more stable 6-fold coordination geometry by binding two extraframework water molecules during hydration. In the presence of ammonia, tetrahedral Cr3+ readily transforms into a 5-fold coordination geometry by binding one ammonia molecule. Therefore, depending on the environmental conditions, the Cr3+ ions can occur in a 4-, 5-, or 6-fold coordination. This observation underlines the flexibility of transition metal ions, such as Cr3+, to cope with unusual coordination geometries in inorganic hosts, making them interesting as potential active sites in heterogeneous catalysis.

Regular intergrowth in the AFI-type crystals: influence on the intracrystalline adsorbate distribution as observed by interference and FTIR-microscopy.

Interference microscopy and FTIR microscopy are applied to study intracrystalline concentration profiles of methanol in CrAPO-5 zeolite crystals. By using both techniques, the high spatial resolution of interference microscopy is complemented by the ability of FTIR spectroscopy to pinpoint adsorbates by their characteristic IR bands. For the first time two-dimensional concentration profiles of an unprecedented quality are reported which show a nonhomogeneous distribution of adsorbate in zeolite crystal under equilibrium with the adsorbate vapor. These nonhomogeneous profiles are attributed to regular intergrowth effects in CrAPO-5. A possible internal structure of CrAPO-5 crystals is suggested.