1,721,079 research outputs found
Structure prediction of crystals, surfaces and nano-particles
No full textWe review the current techniques used in the prediction of crystal structures and their surfaces and of the structures of nanoparticles. The main classes of search algorithm and energy function are summarized, and we discuss the growing role of methods based on machine learning. We illustrate the current status of the field with examples taken from metallic, inorganic and organic systems. This article is part of a discussion meeting issue 'Dynamic in situ microscopy relating structure and function'.</p
A Theoretical Study of Alkali Metal Intercalated Layered Metal Dichalcogenides and Chevrel Phase Molybdenum Chalcogenides
Get PDFThesis (Ph.D. (Engineering mechanics)) --University of Limpopo, 2004This thesis explores the important issues associated with the insertion of Mg2+ and Li+ into the solid materials: molybdenum sulphide and titanium disulphide. This process, which is also known as intercalation, is driven by charge transfer and is the basic cell reaction of advanced batteries. We perform a systematic computational investigation of the new Chevrel phase, MgxMo6S8 for 0 ≤ x ≤ 2, a candidate for high energy density cathode in prototype rechargeable magnesium (Mg) battery systems. Mg2+ intercalation property of the Mo6S8 Chevrel phase compound and accompanied structural changes were evaluated. We conduct our study within the framework of both the local-density functional theory and the generalised gradient approximation techniques. Analysis of the calculated energetics for different magnesium positions and composition suggest a triclinic structure of MgxMo6S8 (x = 1 and 2). The results compare favourably with experimental data. Band-structure calculations imply the existence of an energy gap located ~1 eV above the Fermi level, which is a characteristic feature of the electronic structure of the Chevrel compounds. Calculations of electronic charge density suggest a charge transfer from Mg to the Mo6S8 cluster, which has a significant effect on the Mo-Mo bond length.
There is relatively no theoretical work, in particular ab initio pseudopotential calculations, reported in literature on structural stability, cations "site energy" calculations, and pressure work. Structures obtained on the basis from experimental studies of other ternary molybdenum sulphides are examined with respect to pressure-induced structural transformation. We report the first bulk and linear moduli of the new Chevrel phase structures.
This thesis also studies the reaction between lithium and titanium disulfide, which is the perfect intercalation reaction, with the product having the same structure over the range of reaction 0 x 1 in LixTiS2. Calculated lattice parameters, bulk moduli, linear moduli, elastic constants, density of states, and Mulliken populations are reported.
Our calculations confirm that there is a single phase present with an expansion of the crystalline lattice as is typical for a solid solution, about 10% perpendicular to the basal plane layers. A slight expansion of the lattice in the basal plane is also observed due to the electron density increasing on the sulfur ions. Details on the correlation between the electronic structure and the energetic (i.e. the thermodynamics) of intercalation are obtained by establishing the connection between the charge transfer and lithium intercalation into TiS2. The theoretical determination of the densities of states for the pure TiS2 and Li1TiS2 confirms a charge transfer. Lithium charge is donated to the S (3p) and Ti (3d) orbitals. Comparison with experiment shows that the calculated optical properties for energies below 12 eV agrees well with reflectivity spectra.
The structural and electronic properties of the intercalation compound LixTiS2, for x = 1/4, 3/4, and 1, are also investigated. This study indicates that the following physical changes in LixTiS2 are induced by intercalation: (1) the crystal expands uniaxially in the c-direction, (2) no staging is observed. We also focus on the intercalation voltage where the variation of the cell potential with the degree of discharge for LiTiS2 is calculated. Our results show that it can be predicted with these well-developed total energy methods.
The detailed understanding of the electronic structure of the intercalation compounds provided by this method gives an approach to the interpretation of the voltage composition profiles of electrode materials, and may now clearly be used routinely to determine the contributions of the anode and cathode processes to the cell voltage. Hence becoming an important tool in the selection and design of new systems.
Keywords
Magnesium rechargeable battery; Chevrel, Lithium batteries; Li and Mg-ion insertion; TiS2; Mo6S8; Charge transfer; reflectivity, intercalation, elastic constants, voltage, EOS, Moduli.the National Research Foundation, the Royal Society(U.K),the Council for Scientific and Industrial Research,and Esko
Structure and reactivity of metal ion species in high-silica zeolites
No full textA review; in this chapter, the emphasis moves to reactivity at metal ion sites in zeolites. One of the recent trends in the development of heterogeneous catalysts is connected with metal-contg. zeolites. Metal cations can be introduced into a zeolite at the synthesis stage as well as via various methods of zeolite modification (such as liq.- or solid-state ion-exchange technique, chem. vapor deposition). There are now a no. of unique catalysts (esp. MFI zeolites-based ones) showing high activity and selectivity in the diverse processes. Typical examples of such catalysts and processes are: Ti-contg. zeolites (hydrocarbon oxidn. by hydrogen peroxide); Fe zeolites (direct oxidn. of benzene into phenol by nitrous monoxide); Zn and Ga zeolite (dehydrogenation and aromatization of alkanes) and Cu, Fe, and Co zeolites (SCR of NOx). [on SciFinder (R)
Computer modelling of microporous materials
No full textMicroporous materials, including both zeolites and aluminophosphates are amongst the most fascinating classes of materials, with wide ranging important applications in catalysis, gas separation and ion exchange. The breadth of the field has, moreover, been extended in the last ten years by the discovery of the versatile and exciting ranges of mesoporous materials. Computational methods have a long and successful history of application in solid state and materials science, where they are indeed established tools in modelling structural and dynamic properties of the bulk and surfaces of solids; and where they are playing an increasingly important role in understanding reactivity. Their application to zeolite science developed strongly in the 1980's, with the initial successes in modelling structure and sorption, and with emerging capability in quantum mechanical methods. The field was reviewed over ten years, since then there have been major developments in techniques and of course the power of the available hardware, which have promoted a whole range of new applications to real complex problems in the science of microporous materials. This book aims to summarise and illustrate the current capabilities of atomistic computer modelling methods in this growing field. - Details advances in the rapidly expanding field of microporous materials. - Summarises key current techniques in this type of modelling. - Illustrates the current capabilities of atomistic computer modelling methods
Energy conversion : heterogeneous catalysis
No full textThis chapter illustrates recent advances in computational catalysis by highlighting recent theoretical insights into the mechanism of heterogeneous catalytic systems chosen for their interest to energy conversion processes or reduction of raw material use. The state-of-the-art computational methodologies allow a detailed investigation of highly sophisticated catalytic processes on atomistic models of the catalyst reaction centers that are structurally very close to postulated reality. The first part of the chapter highlights some of the concepts arising from the results obtained by means of computational catalysis, which are now the cornerstones of the physical chemical basis of heterogeneous catalysis. The second part of the chapter discusses chemical reactivity principles for some important heterogeneous catalytic systems
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