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[Display omitted] • On methane dearomatization reaction, two main deactivation modes occurs. • Irreversible damage by zeolite amorphization during the isothermal pre-treatment. • Reversible deactivation by coke deposition ("soft", "hard" and carbide species). • 3 descriptors : coke level, micropore volume loss, monoclinic/orthorhombic change. We report a detailed kinetic study of methane dehydroaromatization on three bifunctional Mo/HZSM-5 catalysts (0.9 wt%, 2.7 wt%, and 17.2 wt% Mo). Two main deactivation modes are present: (i) irreversible damage by zeolite amorphization during the isothermal pre-treatment in an inert atmosphere and (ii) reversible deactivation by coke deposition ("soft", "hard" and carbide species). The former occurs at high Mo loading (>4.0 w%) and provides low activity catalysts. Catalysts with a lower and well-balanced molybdenum loading (<4 w%) suffer mainly from the second deactivation mode. The catalyst decay is modelled by semi-empirical laws including time on stream and coke level. The latter initiates textural and structural catalyst modifications leading to an activity loss. Three deactivation descriptors, 1 : coke level on the spent samples, 2: loss of micropore volume, and 3: monoclinic/orthorhombic phase transition of the zeolite are identified. Further characterization indicates that both molybdenum and carbon species are responsible for the catalytic deactivation of well-balanced catalysts. At least 50% of the initially dispersed molybdenum migrates to the external surface of the zeolite to form large clusters of molybdenum carbide. The coke extracted from the zeolite micropores are confirmed to be mainly unsubstituted polyaromatics. [ABSTRACT FROM AUTHOR]

Abstract: The nanoscale events in an organic-template-free gel leading to the formation of a FAU-type zeolite at 90°C were investigated by transmission electron microscopy (TEM). The study was complemented by ex situ X-ray diffraction (XRD), infrared (IR), 23Na 3Q-MAS NMR, N2 adsorption measurements and chemical analyses. It was found that the critical factor that triggers the growth process and mass transformation from amorphous into crystalline zeolite material is the attainment of a specific level of chemical evolution of the system, expressed in homogenization of the starting gel approaching stoichiometric FAU-type zeolite composition. This period was also marked by the formation and development of voids in the gel particles, containing highly hydrated material transformed later on into negative crystals. The evolution of these areas has been found to be an integral and noteworthy part of the chemical transformation of the gel that preceded the nucleation in the system. The observed transformations in the solid part of the system were induced by sodium, which progressively penetrated in the aluminosilicate matrix, breaking its structure and reorganizing the aluminosilicate species. The sodium behaviour was tracked down by a combination of local and bulk chemical analyses complemented by 23Na 3Q-MAS NMR study. During the initial stage of reaction a growth via propagation through the amorphous network co-existed with the typical solution-assisted hydrothermal crystallization. The later stages of development of the system followed the classical for zeolite-yielding systems crystallization that could be described by the autocatalytic nucleation. [Copyright &y& Elsevier]

Abstract: Previous investigations have shown that an all-silica BEA-type (Si-BEA) material is difficult to be nucleated in basic media and that the fluorosilicic precursors formed in near neutral media play an important role in its formation. The present study reports on the synthesis of this microporous material under basic conditions by using TEA2SiF6 as an additional silica source that provides preformed fluorosilicate species. The effect of the amount of TEA2SiF6 on the purity of the final product, crystallization kinetics and morphological features of Si-BEA were systematically studied. The investigation showed that above a certain concentration corresponding to TEA2SiF6/SiO2 =0.07 pure Si-BEA was obtained and further increase in the concentration improved substantially the crystallization kinetics. The increase in TEA2SiF6 content led also to a gradual increase of the size of the pyramidal (h 0l) face coupled with the decrease of pinacoidal (001) one. Thus, the morphology of the zeolite crystals can be varied from well developed truncated bipyramids to plate-like crystals with dominating pinacoidal faces. A consequence of this morphological changes is the number the pore openings of the channel systems running along the a- and c-axes per total external surface. The framework defectness and water content in the synthesized materials were studied by 29Si NMR spectroscopy and TG analysis, respectively. This combined study revealed that materials with a high level of hydrophobicity, due to the specific effect of fluorine anions, have been synthesized under basic conditions. [Copyright &y& Elsevier]

The effect of room temperature aging on the crystallization rate and size of MFI-type crystals synthesized under high temperature was investigated. First, synthesis mixtures yielding MFI-type zeolite were aged at room temperature for periods of time between 1 and 60 days. This was followed by a rapid synthesis in a pre-heated at 230 °C conventional oven. The utilization of a pre-aged initial systems and high heating rates allowed very rapid synthesis of zeolite. The effect of aging time, crystallization temperature, duration of synthesis and aluminum content on the crystal size and yield was systematically studied. Zeolite nanoparticles with sizes ranging from 130 to 260 nm and relatively narrow particle size distributions were synthesized employing the pure-silica system. The obtained nanocrystals were characterized by X-ray diffraction, scanning electron microscopy, dynamic light scattering and N2 adsorption measurements. [Copyright &y& Elsevier]

This feature article highlights recent developments in nanosized zeolites and addresses the question: what will be next? Until recently the limiting step to practical applications was determined by the challenging synthesis of nanosized zeolites in high yield and adequate form. The advances in the synthesis of nanozeolites that provide the basis for future developments and for diverse practical applications are reviewed. The main trends and challenges in processing, characterization and applications of nanosized zeolites are summarized. Particular attention is paid to the processing of nanosized zeolites in terms of their further use. The extending applications of nanosized zeolites in nanotechnology, medicine, pharmaceutical, and food industry, are discussed. [ABSTRACT FROM AUTHOR]

Zeolite Y and its ultra‐stabilized hierarchical derivative (USY) are the most widely used zeolite‐based heterogeneous catalysts in oil refining, petrochemisty, and other chemicals manufacturing. After almost 60 years of academic and industrial research, their resilience is unique as no other catalyst displaced them from key processes such as FCC and hydrocracking. The present study highlights the key difference leading to the exceptional catalytic performance of USY versus the parent zeolite Y in a multi‐technique study combining advanced spectroscopies (IR and solid‐state NMR) and molecular modeling. The results highlight a hitherto unreported proton transfer involving inaccessible active sites in sodalite cages that contributes to the exceptional catalytic performance of USY. [ABSTRACT FROM AUTHOR]

Zeolite Y and its ultra‐stabilized hierarchical derivative (USY) are the most widely used zeolite‐based heterogeneous catalysts in oil refining, petrochemisty, and other chemicals manufacturing. After almost 60 years of academic and industrial research, their resilience is unique as no other catalyst displaced them from key processes such as FCC and hydrocracking. The present study highlights the key difference leading to the exceptional catalytic performance of USY versus the parent zeolite Y in a multi‐technique study combining advanced spectroscopies (IR and solid‐state NMR) and molecular modeling. The results highlight a hitherto unreported proton transfer involving inaccessible active sites in sodalite cages that contributes to the exceptional catalytic performance of USY. [ABSTRACT FROM AUTHOR]

Abstract: Core–shell zeolite composites possessing a mordenite core and a shell of intergrown silicalite-1 crystals were synthesized. A classical hydrothermal treatment of mordenite crystals with a silicalite-1 precursor mixture did not result in the formation of an extended silicalite-1 layer on the mordenite surface. The incompatibility between the core crystals and the shell precursor was circumvented by adsorption of nanoseeds on the core surface, which upon a subsequent hydrothermal treatment induced the formation of a well intergrown shell. The kinetics of shell growth was studied at 150 and 200°C and the optimum conditions further used for the preparation of composites subjected to XRD, SEM, TG/DTA, EDS and X-ray fluorescence analyses. The integrity of the shell layer was tested by N2 adsorption measurements on materials comprising Na- and Na,H-mordenite and a non-calcined tetrapropylammonium (TPA)-containing shell, the latter being non-permeable for the N2 molecules. These measurements showed that 96–98% of the mordenite crystals were covered with a defect-free TPA-silicalite-1 shell after a single hydrothermal treatment. A characteristic feature of the obtained composites is the relatively large single crystal core and the very thin polycrystalline shell. Thus, the relatively large active part of the composite is covered by a tiny shell that ensures fast kinetics. [Copyright &y& Elsevier]

The zeolite community spent 50 years in pursuing the synthesis of high-silica LTA -type zeolites, and ultimately succeeded with the pure-silica polymorph by applying specific structure-directing agents (SDA). The high-silica zeolite A has exhibited unique properties and strong potential to be applied as an adsorbent and catalyst in several novel processes. In the present study, the high-silica polymorphs of Si/Al ratios from 15 to ∞ were synthesized and subjected to thorough characterizations using multiple physicochemical methods. It has been revealed that there exists strong interactions between the organic SDAs and the framework. Therefore, removing the SDAs by calcination in air is difficult, and can only be done above 700 °C with a certain degree of framework dealumination. The retained framework structure shows connectivity defects and a unique combination of Brønsted and Lewis acidity. Using methanol-to-olefins (MTO) as a probe reaction, the catalytic performance of high-silica LTA -type zeolites has been evaluated. Compared to the well-studied CHA and MFI -type catalysts, high-silica zeolite A exhibited a shorter life-time and higher selectivity towards C 4 olefins, while methane selectivity increased with the deactivation. [Display omitted] • The crystallization of high-silica LTA -type zeolites requires specific structure-directing agents (SDAs). • Strong SDA/framework interactions are evidenced by XRD, NMR and TG. • Complete removal of SDA by calcination accompanied by framework dealumination, while the framework structure retained. • High-silica LTA-type material possesses unique acidity that renders different catalytic performances in MTO reactions. [ABSTRACT FROM AUTHOR]

Chemical interactions occurring between zeolites and alumina binders during the critical steps of catalyst forming are the focus of this study. Three widely used and commercially significant variants of FAU zeolite, covering a wide range of Si/Al ratios, micro- and meso-porosity and acidic properties (Y [LZY-64, Si/Al = 2.3] and USY [CBV 720 and CBV 760 with Si/Al = 16 and Si/Al = 28, respectively]) were shaped by extrusion with pseudoboehmite to produce bound extrudates. These extrudates were characterized by conventional techniques (XRD, 27Al NMR and IR spectroscopy, N 2 physisorption ...) and compared to their parent powders activated under the same conditions. The catalytic performances of the zeolite powders, their derived alumina extrudates and physical zeolite/γ-Al 2 O 3 mixtures were also evaluated employing two different reactions: i) n-octane hydroisomerization, to probe all catalytic sites and ii) 1,3,5 tri-isopropyl benzene dealkylation to probe only the external/mesoporous surfaces. The bound zeolites systematically displayed catalytic performance superior to their parent powders or physical mixtures, especially in the dealkylation of 1,3,5 tri-isopropyl benzene. Infrared spectroscopy measurements of the number, nature and strength of the acid sites were consistent with these catalytic results demonstrating that new catalytic sites are created and located on the external or mesoporous surface of the zeolites, i.e. at the zeolite-binder interface. The work reported here clearly illustrates that binding and subsequent thermal treatment of zeolite powders to produce commercially representative forms can significantly alter the quality and quantity of active sites creating active centers not usually present in pure powders which are typically studied and reported in much of the open literature. Such a study is also a blueprint for other catalytic phases, other forming processes (spray-drying, oil-dropping, pelletizing ...) and could also be applied to the shaping of adsorbents. Image 1 • Zeolite Y were shaped by extrusion using pseudoboehmite as binder. • Acidic properties of zeolite extrudates were probed using basic probe molecule and monitored by infrared. • Zeolite shaping alter qualitatively and quantitatively the acidic properties of the final compounds. • Zeolite Y extrudates systematically displayed catalytic performance superior to their parent powders or physical mixtures, especially in the dealkylation of 1,3,5 tri-isopropyl benzene. • New acid sites are formed during shaping, reminiscent of amorphous silica-alumina. [ABSTRACT FROM AUTHOR]

• Rapid copper sintering occurring under realistic conditions of direct dimethyl ether synthesis. • No copper oxidation under a wide range of dimethyl ether synthesis conditions. • Strong effect of water on copper sintering and crystallite size. Dimethyl ether is one of the most promising environmentally optimized alternatives to the conventional fossil fuels and an important platform molecule for chemical industry. Catalyst deactivation is one of the most important challenges of the single-step dimethyl ether synthesis from syngas. Because of the lack of direct characterization techniques working under harsh reaction conditions, the information about deactivation mechanisms of bifunctional Cu/ZSM-5 catalysts is rather contradictory. In this paper, a combination of synchrotron-based in-situ time-resolved X-ray diffraction and X-ray absorption spectroscopy operating under high pressure and temperature alongside with the conventional ex-situ characterization uncovered very rapid copper sintering occurring under realistic conditions of direct dimethyl ether synthesis. Copper sintering was strongly affected by the presence of water either produced by the reaction or co-fed to the reactor. No copper oxidation was observed under a wide range of experimental conditions. [ABSTRACT FROM AUTHOR]

Surfaces of nano-sized ZSM-5 zeolites have been passivated by a chemical liquid deposition (CLD) technique using tetraethylorthosilicate (TEOS). The impact of this post-synthesis treatment has been evaluated in the methanol-to-olefins (MTO) reaction. A two-step surface passivation led to enhanced selectivity towards C 2 –C 4 light olefins, between 10 and 30% in relative, at nearly complete methanol conversion when compared with pristine zeolites. However, these post-treated zeolites exhibited a significant loss in stability. To rationalize these results and establish structure-activity relationships, zeolite catalysts have been thoroughly characterized by nitrogen adsorption–desorption, SEM, XRF, XRD and FTIR techniques. ZSM-5 zeolite (Si/Al = 27) in the form of well-arranged rectangular nanocrystals behave in MTO after silylation as a commercial ZSM-5 zeolite having a Si/Al = 52. [ABSTRACT FROM AUTHOR]

FER-type zeolites were synthesized in the presence of Na-Ethylendiamine (Na–En), Na–Pyrrolidine (Na–Py) and Na–K. The crystallization times varied between 96 and 240 h. Ferrierite harvested from the Na–En synthesis was also used as seeds and reduced crystallization time from 240 to 30 h. The product of seeded synthesis was not uniform: nanosized with micronsized crystals as well as complex aggregates of different sizes were obtained. Hierarchical FER-type zeolites were prepared using seeded Na–En synthesized FER as a parent. Secondary pores in zeolite crystals were formed by etching at room temperature with HF-NH 4 F containing solutions, using the HF concentration and treatment time as variables. Crystal morphology and physicochemical characteristics of micron-, nano-sized and hierarchical FER-type crystals were studied by complementary methods including: X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry (TG/dTG), 27 Al and 29 Si MAS NMR, IR spectroscopy of adsorbed probe molecules (Pyridine, Acetonitrile and Lutidine), nitrogen adsorption and chemical analysis. We demonstrate that FER-type zeolites with pre-determined properties can be easily prepared. [ABSTRACT FROM AUTHOR]

We used computational modeling, based on Density Functional Theory, to help understand the preference for the formation of silanol nests and the substitution of Si by Ti or Al in different crystallographic positions of the MSE-type framework. All these processes were found to be energetically favorable by more than 100 kJ/mol. We suggested an approach for experimental identification of the T atom position in Ti-MCM-68 zeolite via simulation of infrared spectra of pyridine and acetonitrile adsorption at Ti. The modeling of adsorption of hydrogen peroxide at Ti center in the framework has shown that the molecular adsorption was preferred over the dissociative adsorption by 20 to 40 kJ/mol in the presence or absence of neighboring T-atom vacancy, respectively. [ABSTRACT FROM AUTHOR]

Abstract: A zeolite beta–silicalite-1 composite was prepared by growing polycrystalline silicalite-1 shells on single micron-sized zeolite beta crystals. The obtained core–shell material was employed for the separation of hexane isomers. Gravimetric uptake measurements revealed that the silicalite-1 shell acted as a membrane that controlled the transport to zeolite beta core. The positive impact of the silicalite-1 membrane on the separation of mono- and di-branched hexane isomers was confirmed by breakthrough experiments. The core–shell composite material allowed more selective separation of mono- and di-branched isomers than either of its components alone and had a significantly higher adsorption capacity than silicalite-1. [Copyright &y& Elsevier]

Abstract: Hierarchical porous composite with a core–shell structure possessing FAU-type zeolite core (zeolite X) and LTA-type zeolite shell (zeolite A) has been prepared. The intimate growth of zeolite shell is achieved by in situ crystallization of the LTA zeolite crystals with size of 1μm on large single FAU-type crystals with size of about 60–90μm. Direct visualization of the core–shell material is provided by X-ray microbeam measurements using synchrotron radiation on a single crystal complemented with field emission scanning electron microscopic study. The nitrogen sorption data confirmed that the access to large single FAU-type core is controlled by the defect-free LTA-type shell. Sorption measurements showed that about 98% of core crystals are covered by the LTA shells. Further the FAU–LTA core–shell material is used as a host for the stabilization of platinum clusters. The Pt location, mean size and distribution have been studied by CO chemisorption followed by FT-IR spectroscopy. High loading of platinum accessible to CO molecules in the core–shell material is achieved. The use of the FAU–LTA matrix allowed the stabilization of two different sizes of Pt clusters. Additional advantage of the core–shell material is the protection of the clusters from thermal sintering and poisoning, which is of significant importance for future catalysts. [Copyright &y& Elsevier]

• The use of FER as catalyst for the dehydration of iso-butanol results in an excellent selectivity for n-butenes. • The external Brønsted acid sites function as isobutanol dehydration active sites. • High external Brønsted acidity improves selectivity to n-butenes. • Use of in-situ and operando characterisation toolboxes allowed identifying the active sites. The conversion of isobutanol to light olefins over zeolites was investigated by IR operando spectroscopy. FER zeolites showed a surprisingly high selectivity for the direct conversion of iso-butanol to linear butenes, hence catalyzing dehydration and skeletal isomerization in one step. As a fundamental understanding of the separate reactions is required to design superior catalysts, an in-situ and operando FT-IR mechanistic study of the reaction was carried out. The spectroscopic data, the derived species participating and their respective role are analyzed using chemometric (PCA and MCR-ALS) tools. We highlighted the role played by the external acid sites and the requirement of a specific distance between these sites to ensure the n-butene selectivity and point that the internal Brønsted acidity has an adverse effect on the catalyst stability. Moreover, there is no correlation between the carbon species formed on the surface and the exceptional selectivity towards n-butenes, allowing to exclude a "carbon pool" mechanism. [ABSTRACT FROM AUTHOR]

NH 4 -SSZ-13 is etched with an aqueous solution of 40 w /% NH 4 F under different time/temperature conditions to obtain hierarchical derivatives. The etched zeolites are characterized by XRD, SEM, N 2 physisorption, 29Si/27Al/19F MAS NMR, ICP-AES, and their acidity monitored by in situ FTIR spectroscopy using acetonitrile as a probe molecule. The results highlight that the zeolite is very sensitive to high temperature and high liquid-solid ratio treatments leading to substantial crystallinity losses. These two parameters need careful tuning to obtain hierarchical derivatives retaining important characteristics as micropore volume and framework Si/Al ratio. The catalytic activity of the modified SSZ-13 is evaluated in the n-propanol conversion. Image 1 • Zeolite SSZ-13 (CHA-type) is subjected to chemical etching in an aqueous NH 4 F solution to introduce mesopores. • The hierarchical zeolite preserved the parent zeolite properties in terms of framework composition and Brønsted acidity. • The obtained SSZ-13 derivatives show higher coke contents but slower deactivation in the dehydration of n-propanol. [ABSTRACT FROM AUTHOR]