Synthesis and systematic study of Co₃O₄-based catalysts for oxygen reduction and oxygen evolution reactions

textCo₃O₄-based composite materials are good electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in alkaline solutions. Here, this thesis first investigated the individual functionality of Co₃O₄ and the N-doped carbon nanoweb (CNW) in ORR and OER. The Co₃O₄/CNW bifunctional catalysts were synthesized by an in situ growth of Co precursors onto CNW followed by a controlled heat treatment. Rotating disk electrode measurements were utilized to provide insight into the specific functions of Co₃O₄ and CNW in the composite material during catalysis. It was found that Co₃O₄ alone exhibited poor ORR catalytic activity. However, in the presence of CNW, Co₃O₄ assisted the selective four-electron oxygen reduction over the two-electron pathway. Co₃O₄ acted as the primary catalytic site for OER and CNW improved the electronic conduction between Co₃O₄ and the current collector. CNW underwent serious degradation at the high potential of the OER, but its stability improved greatly upon the deposition of Co₃O₄. Two possible mechanisms for the improved catalytic stability are discussed. The findings demonstrate the specific functions of Co₃O₄ and CNW in catalyzing the OER and ORR and further establish an understanding of the synergy of the composite in electrocatalysis. Based on the critical functionality of Co₃O₄ in stabilizing carbon materials in the OER potential region, it is of interest to investigate novel synthesis methods to prepare nano-sized Co₃O₄ that can provide more active sites for catalytic reactions and thus, improve the OER kinetics. Here, in situ electrochemical generation of 2-dimensional Co₃O₄ (2D-Co₃O₄) nanoplates were achieved by scanning CoO[subscript x]/Co precursors in 1 M KOH solution. X-ray diffraction characterization suggested that CoO[subscript x]/Co precursors were oxidized to Co₃O₄ before the onset potential of OER. Scanning electron microscopy showed that oxidation from CoO[subscript x]/Co to 2D-Co₃O₄ was associated with the formation of hexagonal nanoplates. The 2D-Co₃O₄ exhibited excellent OER catalytic activity and stability probably due to the effective mass transfer through the 2D structure.Materials Science and Engineerin

High order finite difference methods for the wave equation with non-conforming grid interfaces

We use high order finite difference methods to solve the wave equation in the second order form. The spatial discretization is performed by finite difference operators satisfying a summation-by-parts property. The focus of this work is on the numerical treatment of non-conforming grid interfaces. The interface conditions are imposed weakly by the simultaneous approximation term technique in combination with interface operators, which move the discrete solutions between the grids on the interface. In particular, we consider interpolation operators and projection operators. A norm-compatibility condition, which leads to stability for first order hyperbolic systems, does not suffice for second order wave equations. An extra constraint on the interface operators must be satisfied to derive an energy estimate for stability. We carry out eigenvalue analyses to investigate the additional constraint and how it is related to stability, and find that the projection operators have better stability properties than the interpolation operators. In addition, a truncation error analysis is performed to study the convergence property of the numerical schemes. In the numerical experiments, the stability and accuracy properties of the numerical schemes are further explored, and the practical usefulness of non-conforming grid interfaces is presented and discussed in two efficiency studies.Comment: 27 pages, 15 figure

Interactive Blocking in Arrow-Debreu Economies

Competitive behaviors such as outbidding one's rivals may be countered by the rivals' threat of mutually destructive objections. In an Arrow-Debreu model of production economies with firms privatized by property rights, we model such hindered competitive behaviors as a coalition's attempt to block a status quo given the threat that the outsiders of the coalition, especially those with whom the coalition shares ownership of firms, may resort to production-ruining secession. We introduce new concepts of the core such that a coalition's blocking plan is feasible only if it is not blocked by the outsiders with such secession. Based on such notions, we prove core equivalence theorems in the replication framework.core; coalition; core equivalence; blocking; production; firms

Topologies on Types: Connections

For different purposes, economists may use different topologies on types. We char- acterize the relationship among these various topologies. First, we show that for any general types, convergence in the uniform-weak topology implies convergence in both the strategic topology and the uniform strategic topology. Second, we explicitly con- struct a type which is not the limit of any …finite types under the uniform strategic topology, showing that the uniform strategic topology is strictly fi…ner than the strategic topology. With these results, we can linearly rank various topologies on the universal type space, which gives a clear picture of the relationship between the implication of types for beliefs and their implication for behaviors.the universal type space, the strategic topology; the uniform strategic topology; the uniform-weak topology; interim correlated rationalizable actions

Convergence of summation-by-parts finite difference methods for the wave equation

In this paper, we consider finite difference approximations of the second order wave equation. We use finite difference operators satisfying the summation-by-parts property to discretize the equation in space. Boundary conditions and grid interface conditions are imposed by the simultaneous-approximation-term technique. Typically, the truncation error is larger at the grid points near a boundary or grid interface than that in the interior. Normal mode analysis can be used to analyze how the large truncation error affects the convergence rate of the underlying stable numerical scheme. If the semi-discretized equation satisfies a determinant condition, two orders are gained from the large truncation error. However, many interesting second order equations do not satisfy the determinant condition. We then carefully analyze the solution of the boundary system to derive a sharp estimate for the error in the solution and acquire the gain in convergence rate. The result shows that stability does not automatically yield a gain of two orders in convergence rate. The accuracy analysis is verified by numerical experiments.Comment: In version 2, we have added a new section on the convergence analysis of the Neumann problem, and have improved formulations in many place

Core Equivalence Theorem with Production

In production economies, the extent to which non-equilibria are blocked depends on the allocation of control rights among shareholders, because a blocking coalition's resources are affected by the firms it jointly owns with outsiders. We formulate a notion of blocking that takes such interdependency problem into account, and we prove an analog of the Debreu-Scarf theorem for replica production economies. Our theorem differs from theirs in using an additional assumption, which we argue is indispensable and is driven by the interdependency problem.