Search

Metal substitution of molecular sieve systems is a major driving force in developing novel catalytic processes to meet current demands of green chemistry concepts and to achieve sustainability in the chemical industry and in other aspects of our everyday life. The advantages of metal-substituted molecular sieves include high surface areas, molecular sieving effects, confinement effects, and active site and morphology variability and stability. The present review aims to comprehensively and critically assess recent advances in the area of tetra- (Ti, Sn, Zr, Hf) and pentavalent (V, Nb, Ta) metal-substituted molecular sieves, which are mainly characterized for their Lewis acidic active sites. Metal oxide molecular sieve materials with properties similar to those of zeolites and siliceous molecular sieve systems are also discussed, in addition to relevant studies on metal-organic frameworks (MOFs) and some composite MOF systems. In particular, this review focuses on (i) synthesis aspects determining active site accessibility and local environment; (ii) advances in active site characterization and, importantly, quantification; (iii) selective redox and isomerization reaction applications; and (iv) photoelectrocatalytic applications.

Selective hydrogenation catalysts play a key role in many industrial processes, but they are primarily based on supported noble metals, such as Pt and Pd, which are usually dispersed in nanoparticles. However, the production and recovery of these noble metal nanoparticles is a very energy-consuming and expensive procedure. Accordingly, replacing these metals by other inexpensive, transition metals such as Fe and Cu without sacrificing the activity and selectivity, will necessarily reduce their production costs. Moreover, zeolites as a support provide the advantage of shape selectivity to the desired product. In this study, we develop an alternative method for preparing hydrogenation catalysts composed of metallic nanoparticles encapsulated into zeolite frameworks through reductive demetallation of Fe-zeolites or Cu/Fe-zeolites with MFI topology. Particularly, the process of reductive demetallation is described using temperature-programmed reduction (TPR) and Mossbauer spectroscopy data. The reductive demetallation of Fe-MFI, consisting of Fe extraction from the zeolite framework and formation of Fe0 nanoparticles, starts at the temperatures above 800 ℃ and finishes at 1030 ℃, when sintering occurs strongly. In contrast, introduction of second metal leads to the decrease in the reduction temperature, as process of CuFe@MFI formation finishes at 800 ℃. Both Fe@MFI and CuFe@MFI show activity in p-nitrotoluene hydrogenation to p-toluidine. Conversion of the substrate grows with increase in the Cu and Fe loading. Thus, this synthesis method of encapsulation of Fe0 nanoparticles and Fe0-Cu0 bimetallic nanoparticles into the zeolite micropores through reductive demetallation of Fe-zeolites can be used to prepare hydrogenation catalysts.

Nanoporous crystalline aluminosilicates, zeolites, are synthesised by solvothermal method producing three-dimensional (3D) crystals. An alternative, more controllable approach of zeolite synthesis - ADOR – can be used for preparation of isoreticular zeolites with tuneable porosity. Zeolites porosity allows their wide use as isomerisation catalysts due to their shape selectivity effects. Selective isomerisation of m-xylene towards p-xylene is an industrially important reaction due to a high demand for the latter as a substrate for terephthalic acid production. In this work, we investigated the influence of pore size (shape selectivity effect) on the isomerization of m-xylene using a system of isoreticular Al-containing zeolites. These materials, prepared by ADOR approach (UTL, IPC-7, IPC-2, IPC-6, and IPC-4) had different layers connectivity, and therefore various channel systems. We tracked the influence of the pore systems of ADOR zeolites (8- up to 14-ring channels) on the catalytic performance in gas-phase m-xylene isomerisation. We investigated the crystallinity and interlayer distances, phase purity, textural properties of prepared materials, their crystals morphology, and aluminium content. M-xylene isomerisation was carried out in a fixed-bed reactor at 350 °C. ADOR catalysts were compared with standard ZSM-5 zeolite. We show the dependence of zeolite porosity on the performance in isomerisation of m- to p-xylene. Smaller pore zeolites: IPC-4 (8- and 10-ring channels) and IPC-6 (8-, 10- and 12-ring channels) exhibited the lowest conversions, while the highest conversion and p-xylene yields were observed for IPC-2 (10- and 12-ring channels). Presence of extra-large, 14-ring channels (IPC-7 and UTL) resulted in the drop of selectivity due to the xylene disproportionation.

Extra-large pore zeolites clear the way for the synthesis of fine chemicals and bulky compounds unable to enter the channels of medium- and large-pore zeolites.

Bulky epoxides are industrially produced by organic synthesis in multistep procedures, generating significant amounts of waste products in the process. Efficient catalyst in combination with a simple oxidant (H2O2 or O2) would significantly reduce the waste production. Four types of microporous titanosilicates with extra-large pores (Ti-UTL), and shortened diffusion pathways (L-TS, Ti-MCM-22, and Ti-SPP) were prepared and investigated in the epoxidation of cyclooctene with H2O2 and photocatalytic oxidation using O2. Ti-UTL is a zeolite possessing 14−12-ring channel system. l -TS-1 and Ti-MCM-22 are composed of aggregates of titanosilicate nanosheets with the thickness of ca. 2 nm and hexagonal thin platelets, respectively. Ti-SPP is composed of olive-like aggregates with approximately length of 0.88–1.12 μm and width of 0.44−0.68 μm consisting of intergrown (self-pillared) nanosheets having 13−70 nm in size. In the epoxidation with H2O2 as an oxidant, Ti-MCM-22 showed the highest catalytic activity due to the wide interlayer space, which enhanced the accessibility of cyclooctene to active titanium site. While, in the photocatalytic epoxidation in the presence of O2 instead of H2O2, Ti-UTL showed the highest activity. The incorporated germanium atoms, which is indispensable component for the construction of extra-large pores, may affect the electronic properties of active titanium species, leading to high photocatalytic activity.

Transitioning towards green chemistry requires designing sustainable processes to produce both inexpensive and environmentally friendly materials capable of catalyzing complex chemical transformations in fine chemistry. In this context, natural silicate-based catalysts stand out as some of the most promising alternatives, yet vermiculites have been mostly overlooked so far, despite their high potential as clay catalysts with high negative layer charge, high number of exchangeable interlayer cations and high Lewis and Bronsted acidity. Thus, this work reports a previously undescribed and unusual reaction between benzaldehyde and dioxane in the presence of natural and ion-enriched (Al3+, Fe3+, Mg2+, Ni2+, Sn4+) vermiculite catalysts. The effects of different vermiculites on the reaction were assessed both at different activation/calcination temperatures (150 °C, 300 °C and 450 °C) and without activation. Regardless of temperature activation, all vermiculites catalyzed C-C bond cleavage, decarbonylation/ decarboxylation and radical oxidative coupling of benzaldehyde and dioxane, albeit in different yields. Non-activated, natural vermiculite provided the highest benzaldehyde conversion (92 %) and benzaldehyde-based selectivity to the coupling product, 1,4-dioxan-2-yl benzoate (11 %). High benzaldehyde conversion rates were observed also in reactions with aluminum-enriched vermiculite (Al-VMT) activated at 150 °C (84 %), providing 10% selectivity to the coupling product, and with iron (III)-enriched vermiculite (Fe-VMT) (38 % benzaldehyde conversion, 12% selectivity). Catalyst calcination prevented the formation of the 1,4-dioxan-2-yl benzoate while simultaneously enhancing benzaldehyde degradation to benzene. Ultimately, this study shows, for the first time, that vermiculites catalyze radical-oxidative coupling, yielding complex structures such as 1,4-dioxan-2-yl benzoate, which can be used as building blocks in fine chemistry.

Porous materials are outstanding catalysts in various reactions using confinement and shape selectivity effects. Unsurprisingly, extensive research has been conducted on zeolites, pillared clays, metal oxides, metal organic frameworks, and mesoporous materials. In particular, selective oxidation of hydrocarbons stands out an important class of reactions, but the ability to avoid over-oxidation remains a challenge. Thus, the present review highlights the latest findings on octahedral and tetrahedral catalytic materials in oxidation reactions, primarily focusing on types of reactive oxygen species and approaches to their investigation, on the incorporation of different heteroatoms (Ti, Sn) into silica matrices for catalytic purposes and corresponding types of reactions and on surface engineering and design of “single-site catalysts”. In addition, composite catalysts for one-pot selective oxidation reactions are reviewed, providing examples from photochemistry including “single-site photocatalysis”, electrocatalysis, and integration of metal complexes with functional solid materials. Ultimately, the end goal of this review is to discuss current state-of-the-art approaches that are being used in the area of selective catalytic oxidations with some novel porous materials. This includes methods that are being used to study mechanistic details as well as new catalysts and new substrates for such oxidations.

This article demonstrates preparation of metal functionalized zeolite catalysts via a new homogeneous solution pathway enabled by the recently reported exfoliation of zeolite MWW into solution of unilamellar nanosheets. The preparation is carried out by mixing solutions of exfoliated MWW monolayers and Pt nanoparticles with initial size of ca 3 nm and isolation of such hybrid catalysts by freeze-drying. Optionally, the MWW layer solutions were purified by dialysis prior to mixing with the metal solution, which turned out to be beneficial for quality and textural characteristics. However, catalytic performance in the model reaction – 3-nitrotoluene hydrogenation, was mostly determined by the Pt level, i.e. at least 0.3%, and less affected by the apparent quality of the final zeolite support. The catalysts revealed agglomeration of the Pt nanoparticles from roughly 3 nm to between 5 and 10 nm.

International audience; Magnetic Fe@Y composites (carbon coated magnetic iron nanoparticles incorporated in Y zeolite) with 5-8 wt% Fe were synthesized and characterized. Overall acidity of the samples ranges between 2.0 and 2.47 mmol/g and is given mostly by Lewis acid sites. The obtained materials were proven to catalyze the hydrolysis of Ulvan polysaccharide with high conversions. The distribution of the reaction products depends on the reaction conditions and the concentration of Ulvan. The catalytic properties-catalytic performances correlations clearly show the acid zeolite Y is the active phase for Ulvan hydrolysis while the iron nanoparticles enable the catalyst separation in a magnetic field. Under oxygen pressure, the selectivity was completely changed to succinic acid. All Fe@Y composites were recycled for 10 times with no change in the catalytic performances after a simple magnetic separation and washing with water.

The present review covers applications of metal organic frame-works (MOFs) in sensors. Particular attention is paid to gas sensors, since MOFs have demonstrated a good selectivity towards the adsorption of gas molecules. The applications of MOFs as pre-concentrators of the compounds to be analyzed are also outlined. Two modes of operation can be used in the considered sensors: photoluminescent and electrochemical ones.

The zeolite activity in processes driven by Bronsted acid sites is determined by the distribution of the protons in the zeolite and strength of their interaction with the framework. This study aims to assess how much the transformation from three-dimensional (3D) bulk zeolite to its corresponding two-dimensional (2D) layered form changes the proton distribution and strength of the proton-framework interaction and thus how much it affects the zeolite Bronsted acid strength. Zeolites with three distinct topologies, MWW, PCR, and MFI, which form also layered analogues with considerably different thickness and silanol density were considered. To probe the Bronsted acidity of both 3D and 2D forms, an array of typical acidity descriptors (i.e., O-H stretching frequency, shift of O-H frequencies upon adsorption of CO probe molecule, C-O stretching frequencies and adsorption enthalpies of the CO adsorption complex) have been evaluated, employing both dispersion-corrected density functional theory and Fourier-transform infrared spectroscopy. Using these descriptors, the Bronsted acidity of 2D form is, on average, the same or just slightly lower than that of the 3D form. Transformation to layered form does affect the proton distribution and values of acidity descriptors for individual T sites, however, if all T sites are considered, the aggregate effect is almost negligible. Hence, these results suggest that a larger effect of the 3D -> 2D transformation can be expected for frameworks with fewer distinct T sites.

International audience; The NH4F etching is a chemical approach for the preparation of hierarchical zeolites without substantial modification of their framework composition and acidic properties. We employed this approach to modify the 2-dimensional form of ZSM-5 and obtain a catalyst for bulky molecules conversion. The etching conditions were varied in order to obtain hierarchical ZSM-5 with different level of dissolution. Thus, obtained derivatives of 2-dimensional ZSM-5 were thoroughly studied in order to get deep insights into the effect of fluoride treatment. The 2-dimensional ZSM-5 was found unexpectedly stable under etching conditions, which is a consequence of the high quality of zeolite crystals containing a limited number of defect zones and misoriented crystalline domains, in contrast to conventional ZSM-5. Fluoride etching was also used to de-pillar 2-dimensional ZSM-5. The morphology and textural properties of the de-pillared ZSM-5 were very similar to those of the parent layered ZSM-5. Accordingly, amorphous and extra-framework species were dissolved first, resulting in the complete removal of extra-framework Al, thereby strengthening the active sites. In summary, the fluoride etching opens the structure of layered ZSM-5 and strengthens its acid sites when combined with dealumination during calcination.

Zeolites have become indispensable materials for chemical industry being applied as detergents, adsorbents and particularly catalysts. Over the past decades this broad research and application field has experienced rapid development. New zeolite structures were synthesized, fundamental knowledge of micro- and mesoporous materials synthesis and characterization was substantially deepened and, consequently, more economical and environmentally acceptable industrial technologies were developped. This chapter summarizes the fundamental as well as practical aspects of zeolite synthesis, the most important properties of zeolites and their implications for practical use together with the main industrial applications. In particular, the attention is focused on zeolite use as adsorbents and catalysts. Zeolite research field was broadened to related materials, including zeotypes, mesoporous molecular sieves, hierarchic systems and metal-organic-frameworks. Synthesis, properties, and application potential of these novel and exciting groups of porous molecular sieves are briefly highlighted as well. Keywords: Zeolites; Mesoporous materials; Hierarchic systems; Catalysis; Adsorption

Titanium-containing zeolite-based catalysts have been synthesized and investigated as catalysts in methyl(phenyl)sulfide oxidation with hydrogen peroxide. A hierarchical TS-1 prepared by the secondary templating and a layered TS-1 without and with silica and silica-titania pillars have been studied. Conventional TS-1 was a benchmarking material. The study focuses on observation of the different catalytic performance with regard to textural properties; presence and volume of mesopores and different diffusion characteristics. Thus, a deficiency and excess of the oxidizing agent were used in the catalysed reactions and the progress of reaction and selectivity to products were studied. All tested catalysts have shown after 240 min almost total conversion of methyl(phenyl)sulfide with different selectivity (substrate/catalyst mass ratio 10). It was observed that the reactants ratio hydrogen peroxide/ methyl(phenyl)sulfide influences the selectivity to sulfoxide or sulfone over a particular catalyst. In the case of hydrogen peroxide deficiency experiments (H2O2/sulfide = 0.5 mol/mol) the catalysts exhibited different distributions of products. Lamellar catalyst provided 100% selectivity to sulfoxide, the others in range of 90–65% selectivity to sulfoxide; however, the selectivity was independent on the reaction time and substrate conversion. In the case of the excess of the oxidant, except for Ti-pillared TS-1, all the catalysts showed stabile selectivity of 65% towards methyl(phenyl)sulfoxide being independent of the catalyst. The Ti-pillared TS-1 has shown, during the reaction progress, a decrease in the selectivity to sulfoxide from initial 60% to final 20% of sulfoxide at almost total conversion. The only case when higher selectivity to sulfone was achieved was gradual dosing of hydrogen peroxide.

Citronellol is one of the most widely used fragrances for bouquetting purposes and it is a starting material for synthesis of several other terpenoids. Nevertheless, few data have been reported on citronellol selective oxidation. Accordingly, we report our findings on the selective oxidation of citronellol with hydrogen peroxide using a set of titanosilicate catalysts with different morphologies and textural properties&mdash, conventional titanium silicalite 1 (TS-1), mesoporous TS-1, layered TS-1 and silica-titania pillared TS-1 and also studying the effect of the solvent used. Epoxidation of C6=C7 double bond was the main primary reaction in this system and trace signals of C5 allylic oxidation products were observed without formation of citronellal. Due to the presence of post-synthesis introduced additional Ti sites, the silica-titania pillared TS-1 (TS-1-PITi) provided the highest conversion among the tested catalysts, nevertheless, citronellol was oxidized over all the studied catalysts including conventional TS-1, therefore, showing that it penetrates even into MFI micropores (0.55 nm in diameter). When using acetonitrile as a solvent, the conversion was proportional to the titanium content of the catalyst. When studying the effect of the solvent, acetonitrile provided the highest epoxide selectivity (55%) while in methanol, 2-propanol and 1,4-dioxane, ring opening reactions caused epoxide decomposition.

International audience; Titanium silicalite 1 (TS-1) zeolite is an important selective oxidation catalyst. Recently prepared layered and pillared forms expanded the application of TS-1 to the catalytic oxidation of bulky molecules. Despite progress in designing and application of titanosilicate zeolites in catalysis, only qualitative information of their acidity is available. Herein, we report thorough characterization of acid sites in TS-1 zeolites of different morphologies (3D TS-1, layered 2D TS-1, 2D TS-1 pillared either with silica (TS-1-PISi) or silica-titania (TS-1-PITi)) using FTIR spectroscopy and probe molecules. FTIR of adsorbed pyridine was used for quantification of Ti-associated Lewis acid sites based on the integral intensity of υ8a absorption band ca. 1608 cm−1 and measured integrated molar extinction coefficient (ε1608(Ti-LAS) = 0.71 ± 0.01 cm μmol–1). Thermodesorption of pyridine monitored with FTIR showed that distribution of strength of Lewis acid sites is, to some extent, dependent on the way of Ti incorporation in the samples. TS-1-PITi, containing large fraction of external surface Ti(OH)(OSi)3 species introduced post-synthesis, showed increased concentration of stronger Lewis acid centres. FTIR spectroscopy of TS-1 with pre-adsorbed quinoline and d3-acetonitrile probe confirmed enhanced relative concentration of external Lewis acid sites in all layered TS-1 materials (28–38%) vs. 3D TS-1 (2%).

International audience; Fischer–Tropsch synthesis has two main challenges related to direct production of gasoline fuels. First, the chain length distribution of the products follows a broad and unselective Anderson–Schulz–Flory distribution. Second, mostly linear hydrocarbons are formed in the Fischer–Tropsch reaction, thus requiring isomerization while manufacturing gasoline fuels. The present paper addresses a synthetic strategy for the preparation of hierarchical metal and zeolite nanocomposite catalysts for direct synthesis of iso-paraffins from syngas. The nanocomposites are synthesized in three steps. In the first step, the parent (core) zeolite is etched with an ammonium fluoride solution. The etching creates small mesopores inside the zeolite crystals. In the second step, the Ru nanoparticles prepared using water-in-oil microemulsion are deposited in the mesopores of the zeolite. In the third step, a zeolite shell of MFI-type zeolites (silicalite-1 or ZSM-5) is grown on the parent zeolite crystals coating both the etched surface and metallic nanoparticles. Thus, the metal nanoparticles become entirely encapsulated inside the zeolite matrix. Most important parameters such as ruthenium content, zeolite mesoporosity, and more particularly, the acidity of the catalyst shell, which affect the catalytic performance of the synthesized nanocomposite materials in low-temperature Fischer–Tropsch synthesis were identified in this work. The higher relative amount of iso-paraffins was observed on the catalysts containing a shell of ZSM-5. The proximity between metal and acid sites in the zeolite shell of the nanocomposite catalysts is a crucial parameter for the design of efficient metal zeolite bifunctional catalysts for selective synthesis of gasoline-type fuels via Fischer–Tropsch synthesis, while the acidity of the catalyst core has only a limited impact on the catalytic performance.

Research activities and recent developments in the area of three-dimensional zeolites and their two-dimensional analogues are reviewed. Zeolites are the most important industrial heterogeneous catalysts with numerous applications. However, they suffer from limited pore sizes not allowing penetration of sterically demanding molecules to their channel systems and to active sites. We briefly highlight here the synthesis, properties and catalytic potential of three-dimensional zeolites followed by a discussion of hierarchical zeolites combining micro- and mesoporosity. The final part is devoted to two-dimensional analogues developed recently. Novel bottom-up and top-down synthetic approaches for two-dimensional zeolites, their properties, and catalytic performances are thoroughly discussed in this review.

The incorporation of various metals into the zeolite framework creates opportunities for novel applications, especially in catalysis. The recently developed assembly-disassembly-organisation-reassembly (ADOR) strategy was used to prepare zeolites with IPC-2 (OKO) topology. The layered zeolite precursor (IPC-1P) was modified by incorporating various metals (Al, Zn, Sn, Zr, V, Fe, Hf, and Ti) using a stabilisation process. The resulting materials were characterised by X-ray powder diffraction (XRD), Ar adsorption, scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), inductively coupled plasma optical emission spectroscopy (ICP-OES), and diffuse reflectance UV-Vis spectroscopy (DR-UV-Vis). The acidity of Al-containing IPC-2 materials was assessed by acetonitrile and pyridine sorption followed by FT-IR spectroscopy, showing overall concentrations of acid sites of 0.863 mmol g−1 (acetonitrile) and 0.413 mmol g−1 (pyridine). Titanium containing IPC-2 was examined by selective oxidation of methylphenyl sulfide (MPS) to the corresponding sulfoxide (MPSO). Ti-IPC-2 provided a higher conversion than TS-1 after 60 min (30% and 18% respectively) and showed higher selectivity towards MPSO (77% and 63% respectively). Sn-IPC-2 was tested by Baeyer–Villiger oxidation of norcamphor with aqueous hydrogen peroxide, showing a 3.8% norcamphor conversion and a 1.3% yield of the desired lactone (after 8 h reaction). Therefore, the results reported herein clearly show the successful incorporation of metals into the IPC-2 zeolite framework.

This review article aims to cover the state-of-the-art of titanosilicate catalysts for selective oxidations developed within past seven years. Many elaborated materials (e.g., layered and pillared ...

The Baeyer–Villiger oxidation is an important transformation of ketones into esters and particularly for cyclic ketones to lactones. We report here preparation and catalytic activity of layered Sn–silicate catalysts and mesoporous ordered silica catalysts in this reaction. Sn was introduced by using so-called tin–silica pillaring or by impregnation with a mixture of tetraethylorthosilicate and tin(IV) alkoxide. The prepared catalysts were characterized by XRD, N2 physisorption, SEM, UV/Vis, and inductively coupled plasma optical emission spectroscopy (ICP-OES) techniques and the catalysts were studied in the Baeyer–Villiger oxidation of cyclopentanone, norcamphor, and 2-adamantanone with aqueous hydrogen peroxide. Norcamphor and 2-adamantanone were oxidized easily with selectivity up to 99 %. Sn-MS and IPC-1-SnPI materials exhibited the highest conversions (e.g., norcamphor: Sn-MS 37 %, IPC-1-SnPI 36 % after 8 h vs. Sn-MCM-41 22 %). On the other hand, oxidation of cyclopentanone suffered from product hydrolysis to the corresponding 4-hydroxybutanoic acid.

Lamellar and pillared ZSM-5 materials modified with Mg and Zn oxides were synthesized and tested for in-situ catalytic upgrading of eucalyptus woodchips fast-pyrolysis vapors. The introduction of silica pillars into the lamellar ZSM-5 support led to a higher BET area, but also reduced the overall catalyst acidity. The incorporation of MgO and ZnO occurred with a high dispersion over the zeolitic supports, causing also a significant reduction in the value of their textural properties due to a partial blockage of the zeolite pores. Likewise, the acid features of the zeolitic supports underwent sharp changes by the addition of both MgO and ZnO with a strong decrease in the concentration of the Bronsted and Lewis acid sites present in the parent zeolite, as detected by pyridine adsorption followed FTIR spectroscopy. However, additional Lewis acid sites were created associated to the metal oxides deposited onto the zeolitic supports. Pyrolysis tests were accomplished using a lab-scale downdraft fixed-bed reactor working at atmospheric pressure and a temperature of 500 °C. The use of zeolitic catalysts increased the gas yield, mostly due to the formation of CO and CO 2 , to the detriment of bio-oil production. However, the so obtained bio-oils presented higher quality in terms of H/C and O/C ratios, and larger heating values. The incorporation of MgO and ZnO allowed tailoring the zeolite activity to avoid an excessive cracking of the bio-oil, which in turn resulted in a higher yield of the organic compounds present in the bio-oil, and decreasing the formation of undesired polyaromatic hydrocarbons and coke.

The UTL titanosilicate was prepared together with related lamellar Ti-IPC-1PISi material and zeolites Ti-IPC-2 (OKO) and Ti-IPC-4 (PCR) via top-down synthesis. The titanium can be incorporated to the UTL framework by conventional hydrothermal synthesis and it does not affect the so-called ADOR chemistry of the UTL material. Silica-titania pillaring concept was successfully applied providing very active Ti-IPC-1PITi catalyst for bulky molecules epoxidation with hydrogen peroxide. The textural properties of catalysts prepared can be tuned widely keeping the same crystalline titanosilicate active phase. All the materials were characterised by XRD, nitrogen sorption measurement, SEM, and DR-UV/vis spectroscopy. Ti-IPC-1PITi was the most active catalyst in cyclooctene, norbornene, and linalool epoxidation due to the lowest diffusion constraints and sufficient titanium content. Ti-UTL showed activity similar to Ti-BEA in epoxidation of cyclooctene and it provided different products than other titanosilicates in oxidation of linalool with hydrogen peroxide.

TS-1-based catalysts with different textural features, namely layered TS-1, pillared TS-1, and Ti-pillared TS-1 as well as mesoporous TS-1, were investigated in the liquid-phase epoxidation of methyl oleate as a model compound for plant oil-derived substrates with hydrogen peroxide at 50 °C. While over the TS-1-based catalysts, except Ti-pillared TS-1, an epoxide selectivity of up to 93% is achieved, layered and pillared TS-1 are the most active (the amounts of methyl oleate converted after 5 h per number of Ti-sites are 4.64 mol mol−1 and 4.68 mol mol−1) with an efficiency for H2O2 conversion to the epoxide of 27%. Mesoporous TS-1 and conventional microporous TS-1 exhibit a similar activity (3.64 mol mol−1vs. 3.37 mol mol−1), whereas the mesoporous catalyst most efficiently utilizes H2O2 (39% efficiency). The lowest catalytic activity (0.82 mol mol−1), epoxide selectivity as well as H2O2 efficiency are observed over Ti-MCM-36, possessing mainly octahedrally coordinated Ti-sites. The results demonstrate the importance of accessibility of Ti-sites at external crystal surfaces within layered and pillared TS-1, significantly increasing the epoxidation activity with respect to the number of Ti-atoms present in the catalysts.

Lamellar and pillared ZSM-5 zeolites (L-ZSM-5 and PI-ZSM-5, respectively) were synthesized and tested in the catalytic cracking of low-density polyethylene (LDPE). The introduction of silica pillars into lamellar ZSM-5 caused a high increase in the Si/Al ratio (from 33 up to 64) and the generation of uniform mesopores with a size of about 3.5 nm. Both samples provided quite similar LDPE conversions at the three reaction temperatures investigated (340, 360 and 380 °C) despite the lower concentration of acid sites in PI-ZSM-5, which is assigned to the improved active centre accessibility due to the pillaring treatment. Significant activity was observed even at the lowest temperature, with LDPE conversions in the range 27–36%, which indicates that 2D ZSM-5 zeolites are convenient catalysts for polyethylene cracking. The main products of LDPE catalytic cracking were C2–C5 olefins with a selectivity of 60–70%, denoting that an end-chain cracking mechanism is predominant. 2D ZSM-5 samples were subsequently compared with nanocrystalline (n-ZSM-5) and hierarchical ZSM-5 (h-ZSM-5) zeolites. Pyridine adsorption followed by FTIR measurements showed significant differences in terms of not only acid site concentration but also the Bronsted/Lewis acid distribution among the samples. When the LDPE cracking conversion was referred to the zeolite mesopore/external surface area, a good correlation was observed with the concentration of Bronsted acid sites but not when considering just the Lewis acid sites. This interesting fact suggests that Bronsted acid sites are mainly the active centers for the cracking of the LDPE chains, concluding that in addition to the accessibility, the nature of the acid sites plays a major role in this type of reaction.

The authors acknowledge the Czech Science Foundation (P106/12/G015) for the financial support. Selective oxidation of sulphides is a straightforward method of preparation of organic sulphoxides and sulphones, which are important chemical intermediates and building blocks of pharmaceuticals and agrochemicals. Oxidation of methylphenyl sulphide (MPS), diphenyl sulphide (Ph2S), and dibenzothiophene (DBTH) over lamellar titanosilicate catalysts with the MFI and UTL-derived topology was investigated with hydrogen peroxide as the oxidant. Lamellar titanosilicates combine the advantages of crystalline zeolites and mesoporous molecular sieves due to accessible active sites located on the external surface of their layers. The selectivity of the MPS oxidation to methylphenyl sulphoxide is driven by the diffusion restrictions in the catalyst. A methylphenyl sulphoxide selectivity of 95% at 40% conversion was achieved using the Ti-IPC-1-PI catalyst together with an outstanding TONtot = 1418 after 30 min. The selectivity can be adjusted also by dosing of the oxidant to keep its concentration low during the reaction. The silica-titania pillared TS-1-PITi catalyst showed the highest potential of the tested catalysts in oxidative desulphuration, easily oxidising the DBTH to dibenzothiothene sulphone. Postprint

The transformation of analcime into the IMF structure during the crystallization of IMF zeolite is presented. IMF zeolite was found to show behavior similar to TUN zeolite, i.e. crystallization at the expense of an intermediate. Analcime which appeared first in the reaction mixture was further transformed into the IMF structure for aluminosilicate gels with the initial Si/Al ratio in the range of 15–20, i.e. under conditions being optimal for the synthesis of pure IMF phase and also even when seeding the final gel. The effect of synthesis conditions (Si/Al ratio, temperature, time) on the course of crystallization and properties of the high-silica IMF zeolite was investigated and compared with analcime (having the same Si/Al ratio) prepared from clear solutions not containing any organic template and using the same sources of silicon and aluminum as for the synthesis of IMF. The detailed characterization of prepared samples during crystallization is presented.

Titanium containing extra-large pore zeolite CIT-5 (IZA code: CFI) was successfully prepared by direct synthesis using Cab-O-Sil M5 and titanium(IV) butoxide in the presence of LiOH. N -Methylsparteinium hydroxide was used as a structure directing agent. The product crystallized into thin plate crystals with an approximate size of 20 × 5 × 0.2 μm. The lowest achieved Si/Ti ratio was 23. The necessary duration of hydrothermal synthesis increased with increasing concentration of Ti in the reaction mixture from 11 days (Si/Ti = 63 in product) to 17 days (Si/Ti = 36) at 155 °C. Prepared Ti-CFI samples exhibit BET surface areas in the range of 308–346 m 2 /g and micropore volumes of 0.094–0.097 cm 3 /g. CFI possesses extra-large pores (14-ring, 7.2 × 7.5 A) accessible for bulky molecules, therefore, Ti-CFI is a useful catalyst for epoxidation of double bonds in bulky molecules used in perfumery and pharmacy. The Ti-CFI samples proved to be catalytically active in epoxidation of 1-octene, cyclooctene, α-pinene, and norbornene with hydrogen peroxide as oxidation agent.

The crystallization of zeolite TUN with 1,4-bis(N-methylpyrrolidinium)butane as template proceeds through an intermediate, designated IPC-3P, following the Ostwald rule of successive transformations. This apparently layered transient product has been thoroughly investigated and found to consist of MWW monolayers stacked without alignment in register, that is, disordered compared with MCM-22P. The structure was confirmed based on X-ray diffraction and high-resolution (HR)TEM analysis. The layered zeolite precursor IPC-3P can be swollen and pillared affording a combined micro- and mesoporous material with enhanced Brunauer-Emmett-Teller (BET) surface area (685m(2)g(-1)) and greater accessibility of BrOnsted acid sites for bulky molecules. This mesoporous material was probed with 2,6-di-tert-butylpyridine (DTBP). IPC-3P and its modification create a new layered zeolite sub-family belonging to the MWW family. FTIR data indicate that (Al)MWW materials MCM-22 and IPC-3 with Si/Al ratios greater than 20 exhibit a lower relative ratio of BrOnsted to Lewis acid sites than MCM-22 (with Si/Al ratios of around 13), that is, less than 2 versus more than 3, respectively. This is maintained even upon pillaring and warrants further exploration of materials like IPC-3P with a higher Al content. The unique XRD features of IPC-3P indicating misaligned stacking of layers and distinct from MCM-22P, are also seen in other MWW materials such as EMM-10P, hexamethonium-templated (HM)-MCM-22, ITQ-30, and UZM-8 suggesting the need for more detailed study of their identity and properties. Postprint

A new [Ru(II)( η 6 - p -cymene)(1 R ,2 R )- N -((1 S ,2 S )-borneol-10-sulfonyl)-1,2-diphenylethylenediamine] catalyst for the asymmetric transfer hydrogenation of both 1-alkyl and 1-aryl dihydroisoquinolines has been isolated. For the first time in this type of reaction, the catalyst employs an N-alkylsulfonyl group instead of N-arylsulfonyl.

The asymmetric transfer hydrogenation of five dihydroisoquinolines (DHIQs) was studied by NMR spectroscopy. The DHIQs differed by substitution with methoxy groups, which had a significant effect upon the reaction performance in terms of reaction rate and enantioselectivity. The differences are most probably related to the basicity of DHIQs.

We present, to the best of our knowledge, the first parametric study of the asymmetric transfer hydrogenation of imines catalyzed by a Noyori-type catalytic complex based on ruthenium. A model imine for this study was 1-methyl-3,4-dihydroisoquinoline, and a well-known complex RuCl(η 6 - p -cymene)((1 S ,2 S )- N - p -toluenesulfonyl-1,2-diphenylethylenediamine) was chosen as the model catalyst. The reactions were performed in the presence of a formic acid–triethylamine mixture as the source of hydrogen. The parameters examined include general parameters, for example, concentration, temperature, and substrate-to-catalyst molar ratio, as well as parameters specific to this particular reaction, such as the amount of the hydrogenation mixture used, the ratio of its components, or the inhibitive effect of carbon dioxide. During this study, several unexpected parameters worth further investigation have emerged.

A method for the analysis of the optical purity of a series of chiral substituted tetrahydroisoquinolines (THIQs) was developed. The method is based on pre-column derivatization of the analytes with the derivatization reagent (–)-(1R)-menthyl chloroformate. The derivatization reaction selectively gives diastereomeric carbamates that are resolvable on an achiral non-polar GC column. The developed technique covers variously substituted THIQs, which differ significantly in volatility, steric and electronic properties. In all cases, the resolution factors (R) exceeded the value of 1.5. The method represents a robust way of analysis of mixtures of THIQs, which are often present in various matrixes such as body fluids, tissues and reaction mixtures.

A chiral precursor of Mivacurium chloride, (R)-5′-methoxylaudanosine, was prepared using two different methods. The chiral resolution of racemic 5′-methoxylaudanosine, typically used in industry, was carried out in parallel with a procedure consisting of asymmetric transfer hydrogenation (ATH) and reductive methylation. A novel one-pot synthetic step was developed for the synthesis of racemic 5′-methoxylaudanosine. In both routes, the enantioselectivity was high but further purification was necessary to reach the level of a pharmaceutical standard. The individual synthetic steps reported herein can also be used for the synthesis of analogous bistetrahydroisoquinoline-based skeletal muscle relaxants.

Asymmetric transfer hydrogenation of the acyclic imine acetophenone N-benzylimine was studied by means of computational chemistry. Calculated transition states offer an explanation of why this proc...

A highly efficient route for R-1-methyl-tetrahydroisoquinoline preparation comprising Bischler–Napieralski condensation with enantioselective reduction according to the Noyori protocol for cyclic imine intermediate reduction was experimentally explored. The influence of reaction parameters on the activity and selectivity was evaluated. The enhancement of Ru-asymmetric catalyst efficiency (catalyst re-use) was tested—only a small drop of enantioselectivity in consecutive reduction cycles was found.

Density functional theory (DFT) computational methods were used to investigate the increasingly popular ionic mechanistic concept for the asymmetric transfer hydrogenation of imines on the chiral catalyst RuIICl(η6-p-cymene)[(S,S)-N-p-tosyl-1,2-diphenylethylenediamine]. On application of the ionic mechanism, the reaction preferentially affords the (R)-amine product, which is in agreement with the experimental observations. Calculated transition state structures for the hydrogenation of protonated 1-methyl-3,4-dihydroisoquinoline are discussed together with their preceding and following energy minima. Stabilization of the favorable transition state by a CH/π interaction between the η6-p-cymene ligand and the substrate molecule is explored in depth to show that both C(sp2)H/π is more probable than C(sp3)H/π in this molecular system. Finally, transition state geometries for the asymmetric transfer hydrogenation of acetophenone are proposed, which take the “standard” six-membered cyclic form.

Asymmetric transfer hydrogenation (ATH) of cyclic imines using [RuCl(η(6)-p-cymene)TsDPEN] (TsDPEN = N-tosyl-1,2-diphenylethylenediamine) was tested with various aliphatic (secondary, tertiary) and aromatic amines employed in the HCOOH-base hydrogen donor mixture. Significant differences in reaction rates and stereoselectivity were observed, which pointed to the fact that the role of the base in the overall mechanism could be more significant than generally accepted. The hydrogenation mixture was studied by nuclear magnetic resonance (NMR), Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and vibrational circular dichroism (VCD) with infrared spectroscopy. The results suggested that the protonated base formed an associate with the active ruthenium-hydride species, most probably via a hydrogen bond with the sulfonyl group of the complex. It is assumed that the steric and electronic differences among the bases were responsible for the results of the initial ATH experiments.