Selective oxidation of bulky organic sulphides over layered titanosilicate catalysts

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.PostprintPeer reviewe

Selective oxidation of bulky organic sulphides over layered titanosilicate catalysts

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.PostprintPeer reviewe

The Comet Interceptor Mission

Here we describe the novel, multi-point Comet Interceptor mission. It is dedicated to the exploration of a little-processed long-period comet, possibly entering the inner Solar System for the first time, or to encounter an interstellar object originating at another star. The objectives of the mission are to address the following questions: What are the surface composition, shape, morphology, and structure of the target object? What is the composition of the gas and dust in the coma, its connection to the nucleus, and the nature of its interaction with the solar wind? The mission was proposed to the European Space Agency in 2018, and formally adopted by the agency in June 2022, for launch in 2029 together with the Ariel mission. Comet Interceptor will take advantage of the opportunity presented by ESA’s F-Class call for fast, flexible, low-cost missions to which it was proposed. The call required a launch to a halo orbit around the Sun-Earth L2 point. The mission can take advantage of this placement to wait for the discovery of a suitable comet reachable with its minimum ΔV capability of 600 ms−1. Comet Interceptor will be unique in encountering and studying, at a nominal closest approach distance of 1000 km, a comet that represents a near-pristine sample of material from the formation of the Solar System. It will also add a capability that no previous cometary mission has had, which is to deploy two sub-probes – B1, provided by the Japanese space agency, JAXA, and B2 – that will follow different trajectories through the coma. While the main probe passes at a nominal 1000 km distance, probes B1 and B2 will follow different chords through the coma at distances of 850 km and 400 km, respectively. The result will be unique, simultaneous, spatially resolved information of the 3-dimensional properties of the target comet and its interaction with the space environment. We present the mission’s science background leading to these objectives, as well as an overview of the scientific instruments, mission design, and schedule

Reaktivita vnitřních a vnějších Bronstedových kyselých poloh v nanoporézních MFI: kinetická studie H/D výměny

The strength of Bronsted acid sites (BAS) affects the properties of 2D and hierarchical zeolites, but the relative contribution of internal and external BAS remains unknown. Accordingly, this study aims to assess the acidity of external and internal BAS in nanosponge-like MFI zeolites by comparatively analyzing hydrogen-deuterium exchange kinetics between zeolitic deuteroxyl groups and C2H6 molecules monitored by in-situ FTIR spectroscopy. For this purpose, (i) a sample pre-treatment procedure was specifically developed to deuterate only internal or only external acid sites using 2,6-di-tert-butylpyridine (DTBP) as a masking agent and (ii) DFT modeling of surface BAS was performed. Theoretical models of the thin MFI layer revealed that the external surface of MFI crystals contains three types of BAS: (i) BAS positioned in 5-membered rings, either shielded by silanol nests, rendering the site inaccessible for DTBP or yielding a very low adsorption energy for ethane, (ii) BAS pointing into the pores, due to the presence of aluminol, which hinders DTBP accessibility, or the BAS undergoes transformation to a three-coordinate aluminium site, and (iii) BAS accessible to both DTBP and ethane. The results from our kinetics measurements showed that H/D exchange at external BAS of nanosponge MFI zeolites is faster than at internal BAS (rate constants at 425 degrees C: 3.8 10(-3) vs. 2.4 10(-3) s(-1) for external and internal BAS, respectively), but this cannot be attributed to the effect of diffusion. Therefore, the differences in exchange kinetics between external and internal BAS are given by mutual interplay of subtle differences in the corresponding activation barriers (113 vs. 117 kJ/mol for external and internal BAS, respectively) and pre-exponential terms (1.09 10(6) vs. 1.45 10(6) s(-1) for external and internal BAS, respectively).Síla Bronstedových kyselých poloh ovlivňuje vlastnosti 2D a hierarchických zeolitů. Tato studie byla zaměřen na zhodnocení kyselosti vnitřních a vnějších BAS v nanoporézních MFI zeolitech pomocí komparativní analýzy H/D výměny mezi deuteroxylovou skupinou a C2H6 molekulami. Tato výměna byla monitorována pomocí in-situ FTIR spektroskopie. Výsledky byly porovnány s DFT výpočty modelujícími povrchové BAS

Bronstedova kyselost tří- a dvou-dimenzionálních zeolitů

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.Aktivita zeolitů v procesech řízených Bronstedovými kyselými centry je stanovena pomocí distribuce protonů v zeolitu a síly jejich interakce s mřížkou. Tato studie je zaměřena na míru v jaké transformace 3D zeolitů na odpovídající 2D zeolity mění jejich protonovou distribuci a sílu interakce protonů s mřížkou

A New Family of Two-Dimensional Zeolites Prepared from the Intermediate Layered Precursor IPC-3P Obtained during the Synthesis of TUN Zeolite

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.PostprintPeer reviewe

Dust, Field and Plasma instrument onboard ESA's Comet Interceptor mission

International audienceThe main goal of ESA's F-1 class Comet Interceptor mission is to characterise, for the first time, a long period comet; preferably a dynamically-new or an interstellar object. The main spacecraft, will have its trajectory outside of the inner coma, whereas two sub-spacecrafts will be targeted inside the inner coma, closer to the nucleus. The flyby of such a comet will offer unique multipoint measurement opportunity to study the comet's dusty and ionised environment in ways exceeding that of the previous cometary missions, including Rosetta. The Dust Field and Plasma (DFP) instruments located on both the main spacecraft A and on the sub-spacecraft B2, is a combined experiment dedicated to the in situ, multi-point study of the multi-phased ionized and dusty environment in the coma of the target and its interaction with the surrounding space environment and the Sun. The DFP instruments will be present in different configurations on the Comet Interceptor spacecraft A and B2. To enable the measurements on spacecraft A, the DFP is composed of 5 sensors; Fluxgate magnetometer DFP-FGM-A, Plasma instrument with nanodust and E-field measurements capabilities DFP-COMPLIMENT, Electron spectrometer DFP-LEES, Ion and energetic neutrals spectrometer DFP-SCIENA and Dust detector DFP-DISC. On board of spacecraft B2 the DFP is composed of 2 sensors: Fluxgate magnetometer DFP-FGM-B2 and Cometary dust detector DFP-DISC. The DFP instrument will measure magnetic field, the electric field, plasma parameters (density, temperature, speed), the distribution functions of electrons, ions and energetic neutrals, spacecraft potential, mass, number and spatial density of cometary dust particles and the dust impacts. The full set of DFP sensors will allow to model the comet plasma environment and its interaction with the solar wind. It will also allow to describe the complex physical processes including wave particle interaction in dusty cometary plasma

Dust, Field and Plasma instrument onboard ESA's Comet Interceptor mission

International audienceThe main goal of ESA's F-1 class Comet Interceptor mission is to characterise, for the first time, a long period comet; preferably a dynamically-new or an interstellar object. The main spacecraft, will have its trajectory outside of the inner coma, whereas two sub-spacecrafts will be targeted inside the inner coma, closer to the nucleus. The flyby of such a comet will offer unique multipoint measurement opportunity to study the comet's dusty and ionised environment in ways exceeding that of the previous cometary missions, including Rosetta. The Dust Field and Plasma (DFP) instruments located on both the main spacecraft A and on the sub-spacecraft B2, is a combined experiment dedicated to the in situ, multi-point study of the multi-phased ionized and dusty environment in the coma of the target and its interaction with the surrounding space environment and the Sun. The DFP instruments will be present in different configurations on the Comet Interceptor spacecraft A and B2. To enable the measurements on spacecraft A, the DFP is composed of 5 sensors; Fluxgate magnetometer DFP-FGM-A, Plasma instrument with nanodust and E-field measurements capabilities DFP-COMPLIMENT, Electron spectrometer DFP-LEES, Ion and energetic neutrals spectrometer DFP-SCIENA and Dust detector DFP-DISC. On board of spacecraft B2 the DFP is composed of 2 sensors: Fluxgate magnetometer DFP-FGM-B2 and Cometary dust detector DFP-DISC. The DFP instrument will measure magnetic field, the electric field, plasma parameters (density, temperature, speed), the distribution functions of electrons, ions and energetic neutrals, spacecraft potential, mass, number and spatial density of cometary dust particles and the dust impacts. The full set of DFP sensors will allow to model the comet plasma environment and its interaction with the solar wind. It will also allow to describe the complex physical processes including wave particle interaction in dusty cometary plasma

Dust, Field and Plasma instrument onboard ESA's Comet Interceptor mission

The main goal of ESA's F-1 class Comet Interceptor mission is to characterise, for the first time, a long period comet; preferably a dynamically-new or an interstellar object. The main spacecraft, will have its trajectory outside of the inner coma, whereas two sub-spacecrafts will be targeted inside the inner coma, closer to the nucleus. The flyby of such a comet will offer unique multipoint measurement opportunity to study the comet's dusty and ionised environment in ways exceeding that of the previous cometary missions, including Rosetta. The Dust Field and Plasma (DFP) instruments located on both the main spacecraft A and on the sub-spacecraft B2, is a combined experiment dedicated to the in situ, multi-point study of the multi-phased ionized and dusty environment in the coma of the target and its interaction with the surrounding space environment and the Sun. The DFP instruments will be present in different configurations on the Comet Interceptor spacecraft A and B2. To enable the measurements on spacecraft A, the DFP is composed of 5 sensors; Fluxgate magnetometer DFP-FGM-A, Plasma instrument with nanodust and E-field measurements capabilities DFP-COMPLIMENT, Electron spectrometer DFP-LEES, Ion and energetic neutrals spectrometer DFP-SCIENA and Dust detector DFP-DISC. On board of spacecraft B2 the DFP is composed of 2 sensors: Fluxgate magnetometer DFP-FGM-B2 and Cometary dust detector DFP-DISC. The DFP instrument will measure magnetic field, the electric field, plasma parameters (density, temperature, speed), the distribution functions of electrons, ions and energetic neutrals, spacecraft potential, mass, number and spatial density of cometary dust particles and the dust impacts. The full set of DFP sensors will allow to model the comet plasma environment and its interaction with the solar wind. It will also allow to describe the complex physical processes including wave particle interaction in dusty cometary plasma