Quantum Mechanics Studies of Fuel Cell Catalysts and Proton Conducting Ceramics with Validation by Experiment

We carried out quantum mechanics (QM) studies aimed at improving the performance of hydrogen fuel cells. This led to predictions of improved materials, some of which were subsequently validated with experiments by our collaborators.

In part I, the challenge was to find a replacement for the Pt cathode that would lead to improved performance for the Oxygen Reduction Reaction (ORR) while remaining stable under operational conditions and decreasing cost. Our design strategy was to find an alloy with composition Pt3M that would lead to surface segregation such that the top layer would be pure Pt, with the second and subsequent layers richer in M. Under operating conditions we expect the surface to have significant O and/or OH chemisorbed on the surface, and hence we searched for M that would remain segregated under these conditions. Using QM we examined surface segregation for 28 Pt₃M alloys, where M is a transition metal. We found that only Pt₃Os and Pt₃Ir showed significant surface segregation when O and OH are chemisorbed on the catalyst surfaces. This result indicates that Pt₃Os and Pt3Ir favor formation of a Pt-skin surface layer structure that would resist the acidic electrolyte corrosion during fuel cell operation environments. We chose to focus on Os because the phase diagram for Pt-Ir indicated that Pt-Ir could not form a homogeneous alloy at lower temperature. To determine the performance for ORR, we used QM to examine all intermediates, reaction pathways, and reaction barriers involved in the processes for which protons from the anode reactions react with O₂ to form H₂O. These QM calculations used our Poisson-Boltzmann implicit solvation model include the effects of the solvent (water with dielectric constant 78 with pH 7 at 298K). We found that the rate determination step (RDS) was the O_ad hydration reaction (O_ad + H₂O_ad -> OH_ad + OH_ad) in both cases, but that the barrier for pure Pt of 0.50 eV is reduced to 0.48 eV for Pt₃Os, which at 80 degrees C would increase the rate by 218%. We collaborated with the Pu-Wei Wu’s group to carry out experiments, where we found that the dealloying process-treated Pt2Os catalyst showed two-fold higher activity at 25 degrees C than pure Pt and that the alloy had 272% improved stability, validating our theoretical predictions.

We also carried out similar QM studies followed by experimental validation for the Os/Pt core-shell catalyst fabricated by the underpotential deposition (UPD) method. The QM results indicated that the RDS for ORR is a compromise between the OOH formation step (0.37 eV for Pt, 0.23 eV for Pt_2ML/Os core-shell) and H₂O formation steps (0.32 eV for Pt, 0.22 eV for Pt_2ML/Os core-shell). We found that Pt_2ML/Os has the highest activity (compared to pure Pt and to the Pt₃Os alloy) because the 0.37 eV barrier decreases to 0.23 eV. To understand what aspects of the core shell structure lead to this improved performance, we considered the effect on ORR of compressing the alloy slab to the dimensions of pure Pt. However this had little effect, with the same RDS barrier 0.37 eV. This shows that the ligand effect (the electronic structure modification resulting from the Os substrate) plays a more important role than the strain effect, and is responsible for the improved activity of the core- shell catalyst. Experimental materials characterization proves the core-shell feature of our catalyst. The electrochemical experiment for Pt_2ML/Os/C showed 3.5 to 5 times better ORR activity at 0.9V (vs. NHE) in 0.1M HClO₄ solution at 25 degrees C as compared to those of commercially available Pt/C. The excellent correlation between experimental half potential and the OH binding energies and RDS barriers validate the feasibility of predicting catalyst activity using QM calculation and a simple Langmuir–Hinshelwood model.

In part II, we used QM calculations to study methane stream reforming on a Ni-alloy catalyst surfaces for solid oxide fuel cell (SOFC) application. SOFC has wide fuel adaptability but the coking and sulfur poisoning will reduce its stability. Experimental results suggested that the Ni4Fe alloy improves both its activity and stability compared to pure Ni. To understand the atomistic origin of this, we carried out QM calculations on surface segregation and found that the most stable configuration for Ni₄Fe has a Fe atom distribution of (0%, 50%, 25%, 25%, 0%) starting at the bottom layer. We calculated that the binding of C atoms on the Ni4Fe surface is 142.9 Kcal/mol, which is about 10 Kcal/mol weaker compared to the pure Ni surface. This weaker C binding energy is expected to make coke formation less favorable, explaining why Ni₄Fe has better coking resistance. This result confirms the experimental observation. The reaction energy barriers for CHx decomposition and C binding on various alloy surface, Ni₄X (X=Fe, Co, Mn, and Mo), showed Ni₄Fe, Ni₄Co, and Fe₄Mn all have better coking resistance than pure Ni, but that only Ni₄Fe and Fe₄Mn have (slightly) improved activity compared to pure Ni.

In part III, we used QM to examine the proton transport in doped perovskite-ceramics. Here we used a 2x2x2 supercell of perovskite with composition Ba₈X₇M₁(OH)₁O₂₃ where X=Ce or Zr and M=Y, Gd, or Dy. Thus in each case a 4⁺ X is replace by a 3⁺ M plus a proton on one O. Here we predicted the barriers for proton diffusion allowing both includes intra-octahedron and inter-octahedra proton transfer. Without any restriction, we only observed the inter-octahedra proton transfer with similar energy barrier as previous computational work but 0.2 eV higher than experimental result for Y doped zirconate. For one restriction in our calculations is that the O_donor-O_acceptor atoms were kept at fixed distances, we found that the barrier difference between cerates/zirconates with various dopants are only 0.02~0.03 eV. To fully address performance one would need to examine proton transfer at grain boundaries, which will require larger scale ReaxFF reactive dynamics for systems with millions of atoms. The QM calculations used here will be used to train the ReaxFF force field.

Remoção de compostos sulfurados e nitrogenados de diesel hidrotratado por adsorção em argila, alumina e sílica-alumina, impregnadas com metais de transição

Na matriz energética brasileira, o óleo diesel tem lugar de destaque, porém ainda é comercializado com teores de compostos sulfurados e nitrogenados considerados altos para as legislações ambientais que entrarão em vigor nos próximos anos. Tradicionalmente, a remoção desses compostos de enxofre de correntes de petróleo é realizada por processos de hidrotratamento (HDT). No entanto, devido as características do diesel brasileiro, se faz necessária maior severidade para atingir as novas especificações dos combustíveis. Isto implica em investimentos e custos operacionais crescentes para atender a demanda que se instala. Neste contexto, a adsorção está sendo estudada para a purificação da corrente de óleo diesel oriunda da etapa de hidrotratamento como polimento final para alcançar as especificações mais exigentes. Sabe-se que os adsorventes comerciais apresentam limitações na remoção destes contaminantes e uma alternativa que tem se mostrado promissora é a incorporação de metais de transição na estrutura do sólido. No presente trabalho foram modificados adsorventes comerciais, tais como aluminas, sílica-aluminas e argilas pela introdução dos elementos níquel, colbalto e molibdênio e testado o desempenho dessas modificações frente à adsorção de compostos sulfurados e nitrogenados presentes em um diesel hidrotratado. Foram feitas caracterizações químicas, físicas, texturais e morfológicas dos sólidos com e sem incorporação de metais de transição na estrutura original. Os experimentos de adsorção foram realizados a 40C. Avaliando todos os sólidos, o adsorvente que mostrou o melhor desempenho na remoção de compostos sulfurados e nitrogenados por massa de adsorvente foi a sílica-alumina sem modificações, que foi capaz de remover em torno de 90% de compostos nitrogenados e 55 % de sulfurados para 2 g de sólido / 10 mL de diesel. Para os materiais modificados, observou-se que a incorporação dos metais de transição ocasionou redução da sua área superficial e do volume total de poros. Desta maneira, os efeitos esperados pelas interações entre o sítios metálicos e os compostos de nitrogênio e enxofre foram reduzidos

Phase transitions from the solid state of monatomic elements

The principle aims of this thesis include the development of models of sublimation and melting from first principles and the application of these models to the rare gases.

A simple physical model is constructed to represent the sublimation of monatomic elements. According to this model, the solid and gas phases are two states of a single physical system. The nature of the phase transition is clearly revealed, and the relations between the vapor pressure, the latent heat, and the transition temperature are derived. The resulting theory is applied to argon, krypton, and xenon, and good agreement with experiment is found.

For the melting transition, the solid is represented by an anharmonic model and the liquid is described by the Percus-Yevick approximation. The behavior of the liquid at high densities is studied on the isotherms kT/∈ = 1.3, 1.8, and 2.0, where k is Boltzmann's constant, T is the temperature, and e is the well depth of the Lennard-Jones 12-6 pair potential. No solutions of the PercusYevick equation were found for ρσ³ above 1.3, where ρ is the particle density and σ is the radial parameter of the Lennard-Jones potential. The liquid structure is found to be very different from the solid structure near the melting line. The liquid pressures are about 50 percent low for experimental melting densities of argon. This discrepancy gives rise to melting pressures up to twice the experimental values.

Transgressive elements in The Monk: social taboos

A presente dissertação tem como objetivo mostrar como a literatura gótica pode ser atemporal, subvertendo as mentes e conceitos de seus leitores. Partindo do contexto histórico e cultural em que The Monk se inseriu, esse trabalho visa levantar as questões e elementos tão fortemente reprimidos em nossa sociedade desde o final do século XVIII, como as idéias de mal, abjeção e expressão do eu, em um diálogo permanente com a teoria de Michel Foucault, David Punter, Julia Kristeva, entre outros. Desta forma, a análise do romance se dá paralelamente a uma crítica social, visto que a obra gótica tem por um de seus fins denunciar e deslocar a realidade social. Em última instância, será feita a análise algumas personagens do romance e sua respectiva importância na obra

Elements of Decision under Uncertainty with Applications

This work presents the basic elements for the analysis of decision under uncertainty: Expected Utility Theory and its citicisms and risk aversion and its measurement. The concepts of certainty equivalent, risk premium, absolute risk aversion and relative risk aversion, and the "more risk averse than" relation are discussed. The work is completed with several applications of decision making under uncertainty to different economic problems: investment in risky assets and portfolio selection, risk sharing, investment to reduce risk, insurance, taxes and income underreporting, deposit insurance and the value of information.