The search for new materials and the discovery; investigation and synthesis optimization of novel compounds is a central aspect of materials science and inorganic chemistry. In this work, solid-state synthetic techniques were combined with mechanochemical and flux growth methods to optimize the synthesis in three different systems: The family of RE3Fe3Sb7 (RE = La-Nd, Sm, Gd and Tb) compounds, the bismuth telluride bromides BinTeBr (n = 2, 3) and the bismuth bromide Bi5Br4. The former raise ineterst due to their magnetic and thermoelectric properties, respectiveley. The latter represents a new phase in the binary Bi-Br phae diagram.

Thesis. 1976. Ph.D.--Massachusetts Institute of Technology. Dept. of Earth and Planetary Sciences. / Microfiche copy available in Archives and Science. / Vita. / Bibliography: leaves 315-334. / Ph.D.

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<p>Yb2Ti2O7 is one member of a series of magnetic compounds with the pyrochlore lattice structure. For specific types of single-ion anisotropy and exchange interactions, the geometry of the pyrochlore lattice frustrates near-neighbor interactions and coaxes a wide variety of unusual magnetic ground states from such compounds. Yb2Ti2O7 is unique among these compounds in that the source of the frustration is not immediately obvious when one considers the combination of single-ion anisotropy (XY-like) and the nature of the exchange interactions (ferromagnetic) present therein. A conventional magnetic transition was indeed initially expected based on the observation of specific heat anomaly near 200mK. However, many studies produced no signs of long-range magnetic order below this temperature. Intriguingly, above the transition, evidence for unusual two-dimensional correlations came in the form of rods of magnetic diffuse neutron scattering. This thesis contains four articles that detail the results of several neutron scattering studies on Yb2Ti2O7. The goal of these studies was to determine the nature of the static and dynamic spin correlations throughout the magnetic field vs. temperature phase diagram of Yb2Ti2O7.</p> <p>We first performed a time-of-flight neutron scattering experiment on a single crystal of Yb2Ti2O7, which we prepared using the optical floating zone method. This initial study provided a comprehensive survey of the phase diagram, including the previously unexplored response to a magnetic field. We found that the rods of diffuse scattering change qualitatively upon cooling below the temperature of the reported specific heat anomaly, showing signs for the development of short-range three-dimensional correlations. Additionally, we discovered that a relatively small magnetic field applied along the [110] direction could remove the diffuse scattering entirely, and produce sharp spin wave excitations in the inelastic channel, indicating long range spin correlations.</p> <p>We further quantified the temperature dependence of the diffuse scattering in zero-field using a triple-axis neutron spectrometer. The crossover from two-dimensional correlations to short-range three-dimensional correlations was found to begin at 400mK and reach completion near the temperature of the specific heat anomaly, ∼200mK. Our measurements of the low temperature specific heat of several single crystal samples, as well as a powder sample, revealed that significant sample-dependence of the magnetic properties exists. The single crystal samples were shown to have broader features in the specific heat at relatively low temperatures compared to the powder samples, pointing to some amount of structural disorder in the single crystals.</p> <p>To understand the nature of the structural defects in the single crystals, we compared the structure of a crushed single crystal of Yb2Ti2O7 to that of a powder sample using neutron powder diffraction. The major conclusion of that work was that the single crystal is non-stoichiometric, containing 2.3% excess ytterbium on the (non-magnetic) titanium sublattice. The introduction of additional magnetic moments into the system is expected to be the cause of the sample-dependence of the specific heat anomaly.</p> <p>Finally, we fit the spin wave dispersions in the field-polarized state, as measured by time-of-flight inelastic neutron scattering, to an effective spin-1/2 anisotropic exchange Hamiltonian. The microscopic parameters extracted from these fits place Yb2Ti2O7 close to exotic Quantum Spin Liquid phases predicted for the anisotropic spin-1/2 pryochlore model. The exchange parameters also reveal that the source of the frustration in Yb2Ti2O7 comes from the “quantum spin ice” nature of its exchange interactions.</p> / Doctor of Philosophy (PhD)

The fundamental understanding of the dynamic characteristics of metal dissolution and redeposition behavior at the electrode-electrolyte interface is essential, which provides the basis for the development of advanced energy and conversion devices (such as electrochromic devices, electrocatalysts, and batteries) with superior electrochemical performances. We firstly demonstrate the feasibility of resynthesizing the electrode surface chemistry and tuning the electrochemical reactions at the solid-liquid interface by selectively changing the electrolyte composition and electrochemical cycling conditions. Amorphous TiO2 surface layers can be formed on WO3 electrodes by adding exotic Ti cations to the electrolyte, and slow electrochemical cycling. The dissolution and redeposition of electrodes and surface coatings are intertwined, helping to establish a dissolution-redeposition equilibrium at the interface, which can inhibit metal dissolution, stabilize electrode morphology, and promote electrochemical performance. Since the diffusion layer generated by the dissolution of transition metals is ubiquitous at the electrochemical solid-liquid interface, by combining in situ three-electrode electrochemical reaction cell with advanced spatially resolved synchrotron X-ray fluorescence microscopy and micro-X-ray absorption spectroscopy, we then successfully demonstrate the formation and chemical identification of the diffusion layer. By studying the evolution of diffusion layers(tens of micrometers thick) when using WO3 electrodes in acidic electrolytes, we find that with increasing distance of the dissolved species from the electrode surface, the oxidation state remains largely unchanged, but the local electronic environment of the dissolved W species becomes more distorted. We subsequently report a systematic experimental approach by collecting a series of twodimensional fluorescence images at the electrodes to study electrode dissolution and redeposition under different electrochemical conditions. The results show that (1) metal dissolution and redeposition behaviors greatly evolve under different electrode polarization and electrolyte compositions; (2) metal dissolution and redeposition behaviors are independent of bulk electrolyte pH but depend on interfacial pH; and (3) the accumulation of interfacial dissolved species promotes the formation of polytungstate interfacial networks, which ultimately manifest as temporal heterogeneity of redeposition. Lastly, we provide an in-depth study of the underlying mechanism of electrochemicalcycling induced crystallization at the electrode-electrolyte interface through a combination of advanced synchrotron radiation characterization techniques and an in situ electrochemical reaction setup. We have discovered that (1) foreign cations from the electrolyte engender both tensile and compressive strains inside the crystal; (2) repeated electrode dissolution and redeposition promote crystal growth through a non-classical crystallization pathway of particle attachment, but the initial growth of crystals is inhibited by internal strains; and (3) as the strain accumulates, the crystal rotates or moves, which is the fundamental reason for the dynamic structure evolution of the crystal during electrochemical cycling. To our knowledge, this is the first study of electrochemical-cycling-induced crystallization and its strain evolution. These new findings reveal a previously unknown relationship between crystal growth and its internal strain at the electrode-electrolyte interface. / Doctor of Philosophy / Energy drives the entire economy and human civilization. Energy is needed in every aspect of everyday life, and energy is an essential raw material for making and delivering all the products and services that modern society needs, even though it is invisible to us. Since 2000, the global energy demand has increased tenfold and economic growth has spawned a large number of new energy industries, but billions of people are still in urgent need of clean water, sanitation, nutrition, and medical care. Energy is a key factor in meeting these basic requirements for all of humanity. The increasing global energy demand and the increasing impact of climate change have put enormous pressure on the energy market. Therefore, it is necessary to accelerate the relevant actions of energy transition in the world. Among them, the research and innovation of electrochemical energy storage and conversion technology is a major direction. The electrochemical energy storage and conversion technology heavily relies on the various electrochemical reactions in practical devices such as rechargeable batteries, water electrocatalysts, and energy-saving electrochromic smart windows. Within numerous electrochemical reactions under the application, the solid (electrode)-liquid (electrolyte) interface dominates the most important electrochemical reactions. How to understand thephysicochemical reactions at the interface under electrochemical conditions is of great significance. As a major component of research innovations, this research contributes to the design of rational electrode materials, electrolyte compositions, and more efficient and durable electrochemical performance. From a fundamental perspective, my research enriches the understanding of solid-liquid interface reactions under electrochemical conditions, pointing out that electrode dissolution and redeposition and dynamic structural evolution of solid-liquid interfaces are important for further optimizing electrode material design and improving electrochemical performance.

Inorganic nano- and micromaterials (NMMs) exhibit unique properties including high surface areas, tunable optical and electronic properties, low densities, thermal and chemical robustness, and catalytic capabilities, among others. One of the more novel subclasses of NMMs, metal-organic frameworks (MOFs), are crystalline porous coordination polymers consisting of metal nodes connected by organic linkers to form one-, two-, or three-dimensional frameworks. While the mechanism of MOF formation is complex, tuning the metal:ligand ratios, reaction temperature and vessel pressure, ligand concentration, modulator concentration, and H+ activity impacts particle size, morphology, dispersity, and isotropy of these materials. MOFs also exhibit post-synthetic modification capabilities, which, along with their tunable synthetic nature, make them promising candidates for composite materials such as functionalized nanofillers for reverse osmosis (RO) desalination. The work described herein investigates synthetic parameters of a zirconium-based porphyrinic MOF, PCN-222, to selectively control its crystal size, aspect ratio, and dispersity. Size-constrained PCN-222 was post-synthetically modified with fatty acids and zwitterions to be used as RO thin-film composite (TFC) membranes with improved membrane flux, salt rejection, and anti-fouling properties. The synthetic parameters of MOFs were also considered for the commercial scale-up of CO2 direct air capture (DAC) solid sorbents, including UiO-66, MIL-101-Cr, and Mg-MOF-74, to preserve CO2 uptake capacities between lab and industrial scales. / Doctor of Philosophy / Metal-organic frameworks (MOFs) are unique, highly porous materials that have garnered attention for their potential in many applications, including catalysis, drug delivery, energy, and gas storage. In this work, MOFs were produced for environmental applications, particularly for the conversion of salt water to drinkable water in a process known as reverse osmosis (RO) desalination. RO uses a thin membrane to separate dissolved salt, as well as organic materials such as decomposed organisms, from water. Though RO membranes are widely used commercially, they suffer from high costs and short lifetimes; however, their performance is improved through the incorporation of extremely small materials known as nanoparticles. MOF nanoparticles were grown small enough to be dispersed in the polymer matrix of the thin membrane, then functionalized to improve salt rejection and flux, or the speed at which clean water is produced from RO processes. They were also modified to improve lifetimes by preventing the build-up of organic materials on the surface. Besides clean water, MOFs were also prepared for capturing the greenhouse gas, CO2, directly from the air. Because MOFs can be made with many different functionalities, they are promising materials for many different research fields.

The growth of Fe₃O₄ and FeOOH crystals was investigated. Growth modifiers were used to alter the formation of iron oxides from ferrous hydroxide precipitates. Multifunctional carboxylic acids were found to have a strong influence on morphology of FeOOH. Dicarboxylic acids, containing two and seven carbons, changed the characteristics of α-FeOOH. These changes included alteration of the isoelectic point of the particulates and changes in particle size and shape. EDTA was found to alter the phase of FeOOH formation, favoring the synthesis of γ-FeOOH over α-FeOOH at temperatures below 50°C. The effects of multifunctional carboxylic acids were dependent upon the time of addition, and the presence of other growth modifiers. The changes in FeOOH formation were postulated to occur due to interaction between the acid molecules and Green Rust II, a common intermediate in iron oxide growth. The growth of Fe₃O₄ was found to be sensitive to solution pH, and the form of the iron starting materials. Examination of reaction intermediates by x-ray diffraction showed that other Crystalline phases formed prior to the production of Fe₃O₄. Different intermediate phases occurred depending on the amount of hydroxide in the reaction, and differences in Fe³⁺ starting materials. The production of different intermediate phases affected the morphology of Fe₃O₄. Early precipitation of Fe₃O₄ led to small particles, while formation of crystalline Fe(OH)₂ led to large crystals. Formation of a mixture of Green Rust II and Fe(OH)₂ early in the oxidation process led to formation of multiple nuclei, and produced smaller average particles with a wide particle size distribution. Fe₃O₄ particles prepared from α-FeOOH seed crystals were spherical, while Fe₃O₄ particles prepared from FeSO₄ alone were octahedral crystals. / Ph. D.