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Thesis (M.S.)--The University of North Carolina at Greensboro, 2008. / Title from PDF t.p. (viewed May 28, 2009). Advisor: Alice Haddy; submitted to the Dept. of Chemistry and Biochemistry. Includes bibliographical references (p. 104-109).

Thesis (M.S.)--University of North Carolina at Greensboro, 2006. / Title from PDF title page screen. Advisor: Alice Haddy ; submitted to the Dept. of Chemistry. Includes bibliographical references (p. 62-66).

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A successful transition from fossil fuels to renewable energies such as wind and solar will require the implementation of high-energy-density storage technologies. Promising energy storage technologies include lithium-ion batteries, metal-air batteries, and hydrogen production via photoelectrochemical water splitting. While these technologies differ substantially in their mode of operation, they often involve transition-metal oxides as a component. Thus, fundamental materials research on metal oxides will continue to provide much needed advances in these technologies. In this thesis, the electrochemical and electrocatalytic properties of Fe- and Mn-substituted layered LiNiO₂ materials were investigated. These materials were prepared by heating mixed nitrate precursors in O₂ atmosphere at 700-850 °C for 12 h with intermediate grindings. The products were chemically delithiated with NO₂BF₄, and the delithiated samples were annealed at moderate temperatures in order to transform them to a spinel-like phase. Samples were characterized by inductively coupled plasma analysis and Rietveld refinement of the X-ray diffraction patterns, which were found to be in reasonably close agreement regarding lithium stoichiometry. Spinel-like materials were found to possess an imperfect spinel structure when heated at lower temperatures and a significant amount of NiO impurity was formed when heated to higher temperatures. This structural disorder was manifested during electrochemical cycling -- only Mn-rich compositions showed reversible capacities at a voltage of around 4.5 V. The layered materials exhibited significant capacity loss upon cycling, and this effect was magnified with increasing Fe content. These materials were further investigated as catalysts for the oxygen evolution reaction (OER). All samples containing Mn exhibited low OER activity. In addition, delithiation degraded catalyst performance and moderate temperature annealing resulted in further degradation. Because delithiation significantly increased surface area, activities were compared to the relative to BET surface area. Li₀.₉₂Ni₀.₉Fe₀.₁O₂ exhibited significantly higher catalytic activity than Li₀.₈₉Ni₀.₇Fe₀.₃O₂. This prompted testing of Li[subscript x]Ni₁₋[subscript y]Fe[subscript y]O₂ (y = 0, 0.05, 0.1, 0.2, and 0.3) samples. It was found that a Fe content of approximately 10% resulted in the highest OER activity, with decreased activities for both larger and smaller Fe contents. These results were found to be consistent with studies of Fe substituted nickel oxides and oxyhydroxides, suggesting a similar activation mechanism. / text

The oxygen evolution reaction (OER) is kinetically slow and hence a significant efficiency loss in electricity-driven water electrolysis. Understanding the relationships between architecture, composition, and activity in high-performing catalyst systems are critical for the development of better catalysts. This dissertation discusses areas both fundamental and applied that seek to better understand how to accurately measure catalyst activity as well as ways to design higher performing catalysts. Chapter I introduces the work that has been done in the field to date. Chapter II compares various methods of determining the electrochemically active surface area of a film. It further discusses how pulsed and continuous electrodepostition techniques effect film morphology and behavior, and shows that using a simple electrodeposition can create high loading films with architectures that outperform those deposited onto inert substrates. The reversibility of the films, a measure of the films transport efficiency, is introduced and shown to correlate strongly with performance. Chapter III uses high energy x-ray scattering to probe the nanocrystalline domains of the largely amorphous NiFe oxyhydroxide catalysts, and shows that significant similarities in the local structure are not responsible for the change in performance for the films synthesized under different conditions. Bond lengths for oxidized and reduced catalysts are determined, and show no significant phase segregation occurs. Chapter IV seeks to optimize the deposition conditions introduced in Chapter II and to provide a physical representation of how tuning each of the parameters affects film morphology. The deposition current density is shown to be the most important factor affecting film performance at a given loading. Chapter V highlights the different design considerations for films being used in a photoelectrochemical cell, and how in situ techniques can provide information that may otherwise be unobtainable. Chapter VI serves as a summary and provides future directions. This dissertation contains previously published coauthored material.

This work aims to investigate the effects of current density, electrolyte temperature and substrate composition on the morphology of porous anodic films formed on AA 2024-T3 alloy in sulphuric acid electrolytes and the factors that determine the transition between linear and sponge-like film porosities. Comparisons were made with pure aluminium. Particular attention is given to understanding the rising voltage that occurs during galvanostatic hard anodizing of the alloy and the role of oxygen in the anodizing process. Conditions were selected to be representative of typical hard and conventional anodizing processes. SEM was employed to observe the film morphology, which was then correlated with the voltage-time responses. The anodic film composition was investigated by TEM/EDX and SEM/EDX to determine the effect of alloy element enrichment and cell diameter on the distribution of copper species in the film. A real-time gravimetric method was developed to measure the rate of oxygen evolution during anodizing and its influence on the anodizing voltage and film morphology. Results showed that hard anodic films on AA 2024-T3 alloy formed at relatively high voltages have linear pores and cells, contrasting with sponge-like porosity under conventional anodizing. The linear porosity is shown to depend on the voltage, with a morphological transition occurring in the range 25 to 30 V, with linear cells promoted by a high current density and/or low electrolyte temperature. As the film thickens with time, pore blockage by oxygen bubbles, impedes oxidation of the alloy leading to current re-distribution and hence localized increases in the current density producing a rise of the anodizing voltage as anodizing proceeds. The rise of the anodizing voltage, which leads to an increasing call diameter and barrier layer thickness, has a minor influence on the rate of oxygen evolution, which typically consumes about 20 % of the applied current density. In contrast, the voltage rise in the presence of sponge-like films is comparatively negligible, which is suggested to be due to easier escape of oxygen from the film. The films comprising linear cells contain more copper than the sponge-like films, with copper being enriched at the cell boundaries. Moreover, a model is proposed to explain the enrichment of copper, suggesting that above a critical cell diameter, an alloy enrichment sufficient for oxidation of the alloying element can be maintained across the alloy/film interface. Below this diameter, the enrichment is less than that necessary for oxidation, and the alloying element is then incorporated into the film at the cell boundaries.

Controlling catalyst morphology and composition are required to make meaningful structure-activity/stability relationships for the design of future catalysts. Herein, we have employed strategies of presynthesis and infusion or electroless deposition to achieve exquisite control over catalyst composite morphology. The oxygen reduction (ORR) and the oxygen evolution reactions (OER) were chosen as model systems, as their slow kinetics is a major limiting factor preventing the commercialization of fuel cells and rechargeable metal air batteries. In acid, bimetallic (Pt-Cu, Pd-Pt) and monometallic (Pt) catalysts were presynthesized in the presence of capping ligands. Well alloyed Pt-Cu nanoparticles (3-5 nm) adsorbed on graphitic mesoporous carbon (GMC) displayed an ORR activity >4x that of commercial Pt. For both presynthesized Pt and Pt-Cu nanocrystals on GMC, no activity loss was also observed during degradation cycling due to strong metal-support interactions and the oxidation resistance of graphitic carbon. Similar strong metal-support interactions were achieved on non-graphitic carbon for Pd3Pt2 (<4 nm) nanoparticles due to disorder in the metal surface This led to enhanced mass activity 1.8x versus pure Pt, as well as improved stability. For basic electrolytes, we developed an electroless co-deposition scheme to deposit Ag (3 nm) next to MnOx nanodomains on carbon. We achieved a mass activity for Ag-MnOx/VC, 3x beyond the linear combination of pure component activities due to ensemble effects, where Ag and MnOx domains catalyze different ORR steps, and ligand effects from the unique electronic interaction at the Ag-MnOx interface. Activity synergy was also shown for Ag-Pd alloys (~5 nm), achieving up to 5x activity on a Pd basis, resulting from the unique alloy surface of single Pd atoms surrounded by Ag. Lastly, we combined arrested growth of amorphous nanoparticles with thin film freezing to create a high surface area, pure phase perovskite aggregate of nanoparticles after calcination. Sintering was mitigated during the high temperature calcination required to form the perovskite crystals. The high surface areas and phase purity led to OER mass activities ~2.5x higher than the benchmark IrO2 catalyst. / text

Thesis (Ph.D.)--Australian National University, 2002.

The goal of this project is the design of heterogeneous catalysts to facilitate the oxygen evolution reaction (OER). Considering the industrial feasibility for this reaction, first-row transition-metal-based materials are good candidates since they are cheap, abundant and possess variable oxidation states. However, most of them give only moderate catalytic activities, compared with noble-metal-based materials. To achieve efficient catalysts while maintaining low cost, it is important to discover and modify new systems based on the study of existing materials.In chapter 3 we present a study of the effect of surface reduction of birnessite on catalytic activity. A sample of birnessite was reduced by stirring with sodium dithionite, in which case the oxidation states of surface Mn decreased faster than those of inside Mn. We characterized the difference between the oxidation states of Mn of surface and inside (ΔAOS) and further investigate the effect of ΔAOS on catalysis. The catalytic activity was examined by reaction of birnessite samples with ceric ammonium nitrate, and O2 evolution was monitored using a dissolved oxygen probe with respect to time. The most reduced samples with ΔAOS of 0.15 was found to possess a turnover number (TON) of 36 mmol O2 per mol Mn, a value 10-fold higher than the unmodified sample. This result suggests oxidation state differential across layers aids the catalysis. In chapter 4, a more rigorous study is conducted by the examination of few-layer catalysts constructed by manganese oxide sheets with different oxidation states. We stacked low-AOS manganese oxide sheets with high-AOS manganese oxide sheets in various ordered combinations to obtain few-layer birnessite samples with non-uniform distribution of Mn(III). We found samples with more variation in AOS had a lower overpotential (~510 mV) in electrochemical OER catalysis than uniform stacks of the parent manganese oxide sheets (~750 mV for low-AOS sheets, >1000 mV for high-AOS sheets. The result indicates that the distribution of Mn(III) in stacking direction was the dominant factor for OER catalysis in birnessite and is more important than the overall Mn(III) content. We also found the band structures via scanning tunneling microscopy (STM) and provide an electronic-structure-based explanation of the observed activity. In chapter 5 an analogous strategy to that used in chapter 4 is applied to optimize lithium cobalt oxide (LCO) and lithium nickel oxide (LNO) layered catalysts. LCO and LNO contains various oxidation states (or spin states) of cobalt and nickel atoms. With alternatively stacking a high-AOS and a low-AOS cobalt (or nickel) oxide sheets one by one, the electrochemical OER catalytic activity of the obtained few layer LCO (or LNO) sample was enhanced. The results indicated that the structural feature of the alternating distribution of oxidation states affected not only the birnessite catalysts but also both cobalt and nickel oxide materials. In chapter 6 we incorporated both cobalt and nickel oxide sheets into layered heterostructured catalysts. We present findings that mixed transition metal oxide material K-CoxNiyO2 with alternating distribution of cobalt and nickel oxide layers showed enhanced activity mixed Ni-Co metal oxides with homogeneously distributed transition metals. The overpotential of the sample K-Co0.5Ni0.5O2 with alternating distribution of Co and Ni is 460 mV, 190 mV smaller than that of the sample with homogeneously distributed Co and Ni, even though they had a similar elemental composition. / Chemistry