Zhang Lizhi. / "July 2003." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. Ann Arbor, MI : ProQuest Information and Learning Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

Supercapacitors, as promising energy storage devices, have been of interest for their long lifespan compared to secondary batteries, high capacitance and excellent reliability compared to conventional dielectric capacitors. Transition metal oxides can be applied as the electrode materials for pseudocapacitors and offer a much higher specific capacitance. Co3O4 is one of the most investigated transition metal oxides for supercapacitor. Besides simple monometallic oxides, bimetallic transition oxides have recently drawn growing attention in electrochemical energy storage. They present many unique properties such as achievable oxidation states, high electrical conductivities because of the coexistence of two different cations in a single crystal structure. This study focuses on the bimetallic iron cobalt oxide based materials for the application of energy storage. We selected iron as the substituent in spinel Co3O4, by virtue of its abundant and harmless character. Four types of iron cobalt oxides based electrode materials with different morphologies and components have been synthesized for the first time. The hydrothermal method was the main strategy for the synthesis of iron cobalt based materials, which achieved the control of morphology and ratio of components. Multiple characterization methods, including SEM, TEM, XRD, XPS, TGA, BET, have been applied to study the morphologies and nano/submicron structures. The electrochemical properties of as-fabricated samples were performed by electrochemical workstation. In addition, in order to investigate the practical application of electrode materials, asymmetric supercapacitors have been assembled by using as-prepared samples as the positive electrodes and activated carbon as the negative electrodes.

Over the past few years, energy storage devices have received tremendous interest due to the increasing demand for sustainable and renewable energy in modern society. Supercapacitors are considered as one of the most promising energy storage devices because of their high power density and long cycle life. However, low energy density remains as the main shortcoming for supercapacitors. The overall performance of supercapacitors is predominantly determined by the characteristics of the electrodes. Specifically, constructing nanostructured electrode material has been proven as an efficient way to improve the performance by providing large surface area and short ionic and electronic diffusion paths. Another approach to improve the performance of supercapacitors is the rational design of the asymmetric supercapacitor (ASC), which can extend the operation voltage. In this regard, we have focused on the synthesis and utilization of several nanomaterials, in particular, pseudocapacitance materials such as metal oxides and metal phosphides, on both positive and negative electrodes, as well as the ASC design and fabrication. First, three-dimensional TiO2 nanorod arrays have been synthesized on Ti substrate by a facile one-step hydrothermal method and demonstrated as an ideal supercapacitor positive electrode, which exhibited good areal capacitance and excellent cycling stability. Owing to the novel “dissolve and grow” mechanism, this method provides a simple and low-cost technique for flexible supercapacitor application. Second, using cobalt phosphide and iron phosphide as examples, we have demonstrated metal phosphides as high-performance supercapacitor negative electrodes for the first time. Cobalt phosphide nanowire arrays have been synthesized and presented a high capacitance of 571.3 mF/cm2. To improve the cycling stability, gel electrolyte was used to suppress the irreversible electrochemical reaction. The flexible solid-state asymmetric MnO2//CoP supercapacitor exhibited good electrochemical performance, such as a high energy density of 0.69 mWh/cm3 and a high power density of 114.2 mW/cm3. Furthermore, a PEDOT coating has been adapted to further enhance the cycling stability as well as capacitance performance of FeP nanorod arrays. The FeP/PEDOT electrode represents an outstanding capacitance of 790.59 mF/cm2 and a good stability of 82.12% retention after 5000 cycles. In addition, a MnO2//FeP/PEDOT ASC was fabricated with an excellent volumetric capacitance of 4.53 F/cm3 and an energy density of 1.61 mWh/cm3.

Throughout the last half century of materials science, significant motivations came from, and still do, the industrial applications of these materials. Whether it is electronic, thermal, tribological or chemical in nature, the study of metals, semiconductors and insulators eventually reveals that the surface plays a significant part in the properties of these materials. Understanding metal terminations reveals often that an oxide is the stable state of the metallic surface in an ambient atmosphere and the ability to predict and control these oxides has led to significant strides forward in not just the metallic bulk but the oxide as well. Here we add to the understanding of the class of materials known as transition metal oxides by focusing on the structural and chemical nature of their surfaces. Vanadia, chromia and a new mixed metal oxide, VTiO3, all of which form the corundum structure and have physical properties that need further study. Specifically, Cr2O3 has been at the center of much debate over how oxygen chemical potential influences surface terminations and top layer relaxation. Chromia is a wide band gap (~3.4eV) insulator with substantial ligand field interaction and measurements of the 3d states reveal these states split to t2g and eg– consistent with the distorted octahedral. V2O3 is known to be a Mott insulator and paramagnetic, properties that can be modified through dopants, stoichiometry and strain. In this work, solid solutions of V2O3 and Ti2O3 are studied. VTiO3, has been synthesized in a corundum – like structure by epitaxial growth on an isostructural α-Al2O3 substrate. Section I offers a review of corundum like transition metal oxides and their surface properties and motivations of continued research. In section II we describe in detail, the critical components of PLD thin film growth and in the next section a review of the pertinent characterization techniques utilized in the process. Finally, the results are presented of the study of two transition metal oxide structures namely: 1) Novel VTiO3 in a corundum structure has been grown via Pulsed Laser Deposition – Molecular Beam Epitaxy on a single crystal Al2O3(0001) substrate. The sapphire substrate with modest lattice mismatch was utilized in an effort to compel heteroepitaxial growth of the VTiO3 film. Confirmation of the films structure & chemical state were performed by X-Ray diffraction, Transmission Electron Microscopy (HR), X-Ray Photo-electron Diffraction, Ultra-Violet Photo-Electron Diffraction and Reflection High Energy Electron expected that the metal ions exist in a 3+ charge state. While XPS clearly points to a V3+ charge state and this suggests that Ti should as well, however there is also a strong Ti4+ component present. EELS spectra support the existence of a mixed state Ti3+ & 4+. Broadening of the valance band edge as revealed by UPS spectra indicate that the 3d orbitals are occupied and that the a1g molecular states are occupied. The conflict in diffraction data supporting corundum and PES/EELS data suggesting a mixed state implies that additional final state effects are present and/or an oxygen rich structure. 2) Additionally, corundum like Chromium(III) Oxide is formed on a Cr(110) surface and characterized with X-Ray Photoelectron Diffraction, Low Energy Electron Diffraction and XPS for the purpose of characterizing surface termination and terminating layer relaxation. Comparison of the XPD diffraction data with known and previously discussed terminations reveal the as grown film does not conform. Consequently, we propose a new, stoichiometric termination with oxygen termination and 1st layer chromium interstitials. Atop this structure was grown an ultra-thin film of V2O3 by vanadium e-beam evaporation in background oxygen. This final structure supports the previously proposed vanadyl structured surface

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

The elastic properties of novel transition metal oxides have been investigated, using a powerful technique known as Resonant Ultrasound Spectroscopy (RUS). Two sets of transition metal oxides have been studied. One is the ruthenate Ca2-xSrxRuO4 series with a layered perovskite structure, a Mott transition system that connects the Mott insulator Ca2RuO4 with the unconventional superconductor Sr2RuO4. The other set contains geometrically frustrated materials, including vanadium spinels AV2O4 (A = Zn, Mn and Fe) and titanate pyrochlores A2Ti2O7 (A= Y, Tb, Yb, Ho and Dy). The elastic response of five Ca2-xSrxRuO4 single crystals (x = 2.0, 1.9, 0.5, 0.3 and 0.2) has been measured. For 2.0 ≥ x ≥ 0.5, a dramatic softening over a wide temperature range is observed upon cooling, caused by the rotational instability of RuO6 octahedra (for x = 2.0 and 1.9) or the static rotation of the octahedra (for x = 0.5). For the Ca-rich samples (x = 0.3 and 0.2), the softening occurs in a very narrow temperature range, corresponding to the structural phase transition from high-temperature-tetragonal to low-temperature-orthorhombic symmetry. Elastic softening in ZnV2O4 is observed near the cubic-to-tetragonal structural phase transition at 50 K. The elastic response of MnV2O4 is quite unusual, displaying a softening over a wide temperature range with decreasing temperature. Upon cooling, C’ of FeV2O4 becomes so soft that it drops to almost zero around 140 K, where the cubic-to-tetragonal structural transition occurs. For Y2Ti2O7, all three elastic constants show normal “Varshni” behavior. For spin liquid Tb2Ti2O7, all three elastic constants show a pronounced softening below 50 K, indicative of a possible Jahn-Teller, cubic-to-tetragonal transition at very low temperatures. It is also found that the application of a magnetic field suppresses the elastic softening in this compound. Another spin liquid Yb2Ti2O7 shows no elastic softening. The elastic moduli of the spin-ice compounds, Ho2Ti2O7 and Dy2Ti2O7, show a broad “dip” around 100 K, which is believed to be caused by the strong crystal field effect in those two compounds.

Nanostructured materials are materials consisting of nanoparticulate building blocks on the scale of nanometers (i.e. 10-9 m). Composition, crystallinity and morphology can enhance or even induce new properties of the materials, which are desirable for todays and future technological applications. In this work, we have shown new strategies to synthesise metal oxide and metal nitride nanomaterials. The first part of the work deals with the study of nonaqueous synthesis of metal oxide nanoparticles. We succeeded in the synthesis of In2O3 nanopartcles where we could clearly influence the morphology by varying the type of the precursors and the solvents; of ZnO mesocrystals by using acetonitrile as a solvent; of transition metal oxides (Nb2O5, Ta2O5 and HfO2) that are particularly hard to obtain on the nanoscale and other technologically important materials. Solvothermal synthesis however is not restricted to formation of oxide materials only. In the second part we show examples of nonaqueous, solvothermal reactions of metal nitrides, but the main focus lies on the investigation of the influence of different morphologies of metal oxide precursors on the formation of the metal nitride nanoparticles. In spite of various reports, the number and variety of nanocrystalline metal nitrides is marginally small by comparison to metal oxides; hence preformed metal oxides as precursors for the preparation of metal nitrides are a logical choice. By reacting oxide nanoparticles with cyanamide, urea or melamine, at temperatures of 800 to 900 °C under nitrogen flow metal nitrides could be obtained. We studied in detail the influence of the starting material and realized that size, crystallinity, type of nitrogen source and temperature play the most important role. We have managed to propose and verify a dissolution-recrystallisation model as the formation mechanism. Furthermore we could show that the initial morphology of the oxides could be retained when ammonia flow was used instead. / Nanostrukturierte Materialien sind Materialien, die aus nanopartikulären Baueinheiten in der Größenordnung von Nanonmetern (d.h. 10-9 m) bestehen. Zusammensetzung, Kristallinität und Morphologie können die natürlichen Eigenschaften dieser Materialien verbessern oder zusätzliche Eigenschaften erzeugen, die für heutige und zukünftige Anwendungen und Verfahren wünschenswert sind. In dieser Arbeit präsentieren wir neue Strategien zur Synthese von Nanopartikeln der Metaloxide und Metalnitride. Im einführenden Teil wird die nichtwässrige Synthese von Metaloxidnanopartikeln beschrieben. Uns gelang die Darstellung von In2O3 Nanopartikeln, deren Größe und Form wir durch die Wahl des Prekursors und des Lösemittels deutlich beeinflussen konnten; von ZnO Mesokristallen durch den Einsatz von Acetonitril als Lösemittel; von Übergangsmetalloxiden (Nb2O5, Ta2O5 and HfO2), die besonders schwer im Nanomaßstab zu erhalten sind und von anderen, technisch relevanten Materialien. Die Möglichkeiten der solvothermalen Synthese sind nicht mit der Darstellung von Oxidmaterialen erschöpft. Im zweiten Teil zeigen wir einige Beispiele nichtwässriger, solvothermaler Synthese von Metalnitriden auf; das Hauptaugenmerk liegt aber auf einer Betrachtung der Einflüsse der Morphologie von Metaloxidnanopartikelprekursoren auf die Bildung der Metalnitridnanopartikel. Die Anzahl und Vielfalt bekannter nanokristalliner Metalnitride ist verschwindend klein im Vergleich zu den Metaloxiden, die in der Fachliteratur etabliert sind und demzufolge einen reichen Baukasten an Prekursoren zur Darstellung von Metalnitriden liefern. Durch die Reaktion von Metaloxidnanopartikeln mit Cyanamid, Urea oder Melamine bei Temperaturen von 800 bis 900 °C unter Stickstofffluss konnten Metalnitride erhalten werden. Eine detaillierte Studie der Reaktionsbedingungen und des Reaktionsablaufs zeigte auf, dass Größe und Kristallinität der Metaloxide, die Art der Stickstoffquelle und die Temperatur die entscheidenden Faktoren sind und legte eine Auflösungs-Rekristallisation als Modelmechanismus dieser Art Reaktion nahe. Darüber hinaus konnte gezeigt worden, dass die anfängliche Morphologie des Oxids unter einem Ammoniafluss beibehalten werden konnte.

The aim of this study is the synthesis of hydrogen storage compounds by electrodeoxidation technique which offers an inexpensive and rapid route to synthesize compounds from oxide mixtures. Within the scope of this study, two hydrogen storage compounds, FeTi and Mg2Ni, are aimed to be produced by this technique. In the first part, effect of sintering conditions on synthesis of FeTi was studied. For this purpose, oxide pellets made out of Fe2O3-TiO2 powders were sintered at temperatures between 900 &deg / C &ndash / 1300 &deg / C. Experiments showed that by sintering at 1100 &deg / C, Fe2TiO5 forms and particle size remains comparatively small, which improve the reducibility of the oxide pellet. Experimental studies showed that the reduction of MgO rich MgO-NiO oxide pellet to synthesize Mg2Ni occurs only at extreme deoxidation conditions. Pure MgO remains intact after deoxidation. In contrast to these, pure NiO and NiO rich MgO-NiO mixtures were deoxidized successfully to Ni and MgNi2, respectively. Conductivity measurements address the low conductivity of MgO-rich systems as one of the reasons behind those difficulties in reduction. In the last part, a study was carried out to elucidate the low reducibility of oxides. It is considered that the oxygen permeability becomes important when the reduction-induced volumetric change does not yield fragmentation into solid-state. The approach successfully explains why MgO particles could not be reduced at ordinary deoxidation conditions. The study addresses that Mg layer formed at the surface of MgO particles blocks the oxygen transport between MgO and electrolyte as Mg has low oxygen permeability.

Nanopore covered microporous silicon interfaces have been formed via an electrochemical etch for gas sensor applications. Rapid reversible and sensitive gas sensors have been fabricated. Both top-down and bottom-up approaches are utilized in the process. A nano-pore coated micro-porous silicon surface is modified selectively for sub-ppm detection of NH3, PH3, NO, H2S, SO2. The selective depositions include electrolessly generated SnO2, CuxO, AuxO, NiO, and nanoparticles such as TiO2, MgO doped TiO2, Al2O3, and ZrO2. Flow dynamics are analyzed via numerical simulations and response data. A general coating selection method for chemical sensors is established via an extrapolation on the inverse of the Hard-Soft Acid-Base concept.

Die eingereichte Dissertation befasst sich mit Übergangsmetalloxid-Nanostrukturen, wobei quasi-eindimensionale Materialien im Mittelpunkt stehen, z.B. Nanoröhren und Nanostäbe. Mittels Suszeptibilitäts- bzw. EELS-Messungen wurden magnetische und elektronische Eigenschaften verschiedener Nanoverbindungen untersucht. Zur weiteren Charakterisierung der Proben wurden außerdem Magnetisierungsmessungen (VSM, Pulsfeld), optische Spektroskopie, AC-Suszeptibilitätsmessungen, Messungen der spezifischen Wärme sowie NMR- und ESR-Experimente durchgeführt. Ein Schwerpunkt dieser Arbeit sind Vanadiumoxid-Verbindungen, wobei Vanadiumoxid-Nanoröhren (VOxNT) aufgrund ihrer besonderen Morphologie eine Sonderstellung unter den vorgestellten Materialien besitzen. Suszeptibilitätsmessungen an den VOxNT offenbaren aktiviertes Verhalten bei Temperaturen T > 100 K, was auf V4+-Spindimere zurückgeführt werden kann. Zudem existieren quasi-freie V4+-Momente sowie längere Spinkettenfragmente, z.B. Trimere. Elektronische Anregungen im Valenzband können wahrscheinlich dem Platzwechsel von 3d-Elektronen zwischen V4+- und V5+-Plätzen innerhalb der gemischtvalenten V-O-Ebenen zugeschrieben werden. Durch Dotierung mit Alkalimetallen ist es möglich, die V 3d-Niveaus mit zusätzlichen Elektronen zu besetzen und dadurch die Vanadiumvalenz zu beeinflussen (V5+ -> V4+ -> V3+). Die dabei auftretenden stärkeren Coulombabstoßungen zwischen den V 3d-Elektronen beeinträchtigen die Mobilität der Ladungsträger. Ebenso wurde gezeigt, dass sich durch die Dotierung mit Ammoniak und anderen Übergangsmetallionen die Vanadiumvalenz sowie der Magnetismus der VOxNT beeinflussen lassen. Die Ergebnisse von weiteren Vanadiumoxid-Nanostrukturen - Co0.33V2O5, alpha-NaV2O5, VO2(B) sowie V3O7·H2O-Nanokristallen - zeigen, dass sehr unterschiedliches magnetisches Verhalten wie Paarbildung zwischen V4+-Spins, antiferromagnetisch gekoppelte Spinketten oder ein Phasenübergang zwischen zwei paramagnetischen Temperaturbereichen auf Nanoebene realisiert werden kann. Die magnetischen Eigenschaften von MnO2-Nanostäben sind durch starke Kopplungen und Frustration zwischen den Mn-Spins gekennzeichnet. Außerdem zeigt die Verbindung Merkmale eines Spinglases. Durch Dotierung mit Elektronen lässt sich bei diesem Material die Mn-Valenz verändern. Schließlich zeigen erste Charakterisierungsmessungen an übergangsmetalldotierten MoO3-Nanobändern paramagnetisches Verhalten dieser Systeme.