The synthesis, characterization, and proposed mechanism of formation of a new family of silicatelaluminosilicate mesoporous molecular sieves designated as M41S is described. MCM-41, one member of this family, exhibits a hexagonal arrangement of uniform mesopores whose dimensions may be engineered in the range of - 15 A to greater than 100 A. Other members of this family, including a material exhibiting cubic symmetry, have ken synthesized. The larger pore M41S materials typically have surface areas above 700 m2/g and hydrocarbon sorption capacities of 0.7 cc/g and greater. A templating mechanism (liquid crystal templating-LCT) in which surfactant liquid crystal structures serve as organic templates is proposed for the formation of these materials. In support of this templating mechanism, it was demonstrated that the structure and pore dimensions of MCM-41 materials are intimately linked to the properties of the surfactant, including surfactant chain length and solution chemistry. The presence of variable pore size MCM-41, cubic material, and other phases indicates that M41S is an extensive family of materials.

http://dns2.asia.edu.tw/~ysho/ysho-english/1000 wc/pdf/j ame che soc114, 10834.pdf

A new family of mesoporous molecular sieves prepared with liquid crystal templates

Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These

Phd by thesis

Metal–Organic Frameworks for Separations

The introduction of synthetic zeolites has led to a paradigm shift in catalysis, separations, and adsorption processes, due to their unique properties such as crystallinity, high-surface area, acidity, ion-exchange capacity, and shape-selective character. However, the sole presence of micropores in these materials often imposes intracrystalline diffusion limitations, rendering low utilisation of the zeolite active volume in catalysed reactions. This critical review examines recent advances in the rapidly evolving area of zeolites with improved accessibility and molecular transport. Strategies to enhance catalyst effectiveness essentially comprise the synthesis of zeolites with wide pores and/or with short diffusion length. Available approaches are reviewed according to the principle, versatility, effectiveness, and degree of reality for practical implementation, establishing a firm link between the properties of the resulting materials and the catalytic function. We particularly dwell on the exciting field of hierarchical zeolites, which couple in a single material the catalytic power of micropores and the facilitated access and improved transport consequence of a complementary mesopore network. The carbon templating and desilication routes as examples of bottom-up and top-down methods, respectively, are reviewed in more detail to illustrate the benefits of hierarchical zeolites. Despite encircling the zeolite field, this review stimulates intuition into the design of related porous solids (116 references).

Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design.

As the oil reserves are depleting the need of an alternative fuel source is becoming increasingly apparent. One prospective method for producing fuels in the future is conversion of biomass into bio-oil and then upgrading the bio-oil over a catalyst, this method is the focus of this review article. Bio-oil production can be facilitated through flash pyrolysis, which has been identified as one of the most feasible routes. The bio-oil has a high oxygen content and therefore low stability over time and a low heating value. Upgrading is desirable to remove the oxygen and in this way make it resemble crude oil. Two general routes for bio-oil upgrading have been considered: hydrodeoxygenation (HDO) and zeolite cracking. HDO is a high pressure operation where hydrogen is used to exclude oxygen from the bio-oil, giving a high grade oil product equivalent to crude oil. Catalysts for the reaction are traditional hydrodesulphurization (HDS) catalysts, such as Co–MoS2/Al2O3, or metal catalysts, as for example Pd/C. However, catalyst lifetimes of much more than 200 h have not been achieved with any current catalyst due to carbon deposition. Zeolite cracking is an alternative path, where zeolites, e.g. HZSM-5, are used as catalysts for the deoxygenation reaction. In these systems hydrogen is not a requirement, so operation is performed at atmospheric pressure. However, extensive carbon deposition results in very short catalyst lifetimes. Furthermore a general restriction in the hydrogen content of the bio-oil results in a low H/C ratio of the oil product as no additional hydrogen is supplied. Overall, oil from zeolite cracking is of a low grade, with heating values approximately 25% lower than that of crude oil. Of the two mentioned routes, HDO appears to have the best potential, as zeolite cracking cannot produce fuels of acceptable grade for the current infrastructure. HDO is evaluated as being a path to fuels in a grade and at a price equivalent to present fossil fuels, but several tasks still have to be addressed within this process. Catalyst development, understanding of the carbon forming mechanisms, understanding of the kinetics, elucidation of sulphur as a source of deactivation, evaluation of the requirement for high pressure, and sustainable sources for hydrogen are all areas which have to be elucidated before commercialisation of the process.

A review of catalytic upgrading of bio-oil to engine fuels

https://home.uni-leipzig.de/energy/publist/pfeifer1985.pdf

Nuclear magnetic resonance studies on the acidity of zeolites and related catalysts

NMR intensity measurements of half-integer quadrupole nuclei

On weakly rehydrated dealuminated zeolites and amorphous silica–aluminas the presence of different types of acidic centres can be ascertained by proton magic-angle spinning nuclear magnetic resonance (1H MAS NMR) measurements. A 1H NMR line at ca. 6.5 ppm is caused by water adsorption on Lewis-acid sites. The shift of the 1H NMR line of Bronsted-acid sites (bridging OH groups) to lower field for hydrated samples can be interpreted quantitatively by a fast proton exchange between water molecules, bridging OH groups and hydroxonium ions.

Magic-angle spinning nuclear magnetic resonance studies of water molecules adsorbed on Brønsted- and Lewis-acid sites in zeolites and amorphous silica–aluminas

1H MAS NMR studies on the acidity of zeolites

The applicability of nuclear magnetic resonance (NMR) spectroscopy continues to expand in physics, chemistry, material science, geology, biology, and medicine. An increasing range of NMR techniques is employed for either spectroscopic studies or imaging purposes, most becoming possible because of the high magnetic fields of superconducting magnets (almost an order of magnitude higher than ordinary iron magnets), and the availability of fast computers for controlling purposes and final data processing. These improvements together with the realization of fast mechanical sample spinning and new pulse techniques have led to high-resolution solid-state nuclear magnetic resonance. Because the perturbing effect of the electric quadrupole interaction becomes less important at higher magnetic fields, the investigation of powder samples with NMR techniques has become more feasible. As a result, the number of publications concerning NMR studies of quadrupole nuclei in powder samples rapidly increased in the eighties. However, since 1987 this number of publications is rather stable and amounts to about 100 per year.

Dieter Freude

Papers

Nuclear magnetic resonance studies on the acidity of zeolites and related catalysts

NMR intensity measurements of half-integer quadrupole nuclei

Magic-angle spinning nuclear magnetic resonance studies of water molecules adsorbed on Brønsted- and Lewis-acid sites in zeolites and amorphous silica–aluminas

1H MAS NMR studies on the acidity of zeolites

Quadrupole Effects in Solid-State Nuclear Magnetic Resonance