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.

偏振模色散和时延抖动对啁啾光纤光栅色散补偿特性的影响

对存在偏振模色散(PMD)和群时延(GD)抖动的非理想线性啁啾光纤光栅的色散补偿特性进行了研究。实验测量了啁啾光纤光栅的群时延谱和偏振模色散光谱，理论分析和实验测量表明，啁啾光纤光栅差分群时延(DGD)抖动与其时延抖动密切相关。通过数值模拟方法，计算了线性啁啾光纤光栅偏振模色散眼图代价与入射到啁啾光纤光栅色散补偿器的光信号的偏振方向的关系，计算结果表明在使用啁啾光纤光栅色散补偿器时应对光信号的偏振方向进行调整，以获得最佳补偿效果。另外结合实验数据，模拟计算并讨论了非理想线性啁啾光纤光栅群时延抖动和偏振模色

Anomalous electric dipole internal conversion

Electric dipole internal conversion has been experimentally studied for several nuclei in the rare earth region. Anomalies in the conversion process have been interpreted in terms of nuclear structure effects. It was found that all the experimental results could be interpreted in terms of the j ∙ r type of penetration matrix element; the j ∙ ∇ type of penetration matrix element was not important. The ratio λ of the El j ∙ r penetration matrix element to the El gamma-ray matrix element was determined from the experiments to be:

Lu¹⁷⁵,396 keV, λ = - 1000 ± 100;

282 keV, λ = 500 ± 100;

144 keV, λ = 500 ± 250;

Hf¹⁷⁷, 321 keV λ = - 1400 ± 200;

208 keV λ = - 90 ± 40;

72 keV |λ| ≤ 650;

Gd¹⁵⁵, 86 keV λ = - 150 ± 100;

Tm¹⁶⁹, 63 keV λ = - 100 ± 100;

W¹⁸², 152 keV, λ = - 160 ±80;

67 keV, λ = - 100 ± 100.

Predictions for λ are made using the unified nuclear model.

Entre a negação e a possibilidade: um estudo discursivo da fala do professor sobre o seu trabalho

Esta pesquisa se propõe a analisar a fala de professores de Língua Portuguesa da rede municipal de ensino do Rio de Janeiro sobre o seu trabalho, inserido num período de mudanças para essa rede de ensino. Para tal, foi realizado um grupo de discussão (GD), um momento coletivo de fala dos professores sobre o seu trabalho, através do qual se verificou a expressiva incidência de enunciados negativos de caráter polêmico, segundo definição de Ducrot (1987). Assim, tais enunciados e seus respectivos pontos de vista subjacentes formaram o corpus da pesquisa. Buscou-se, a partir desse recorte, refletir sobre os discursos que circulam sobre o trabalho docente, relacionando-os aos conceitos de competências (SCHWARTZ, 1998), renormalizações (SCHWARTZ, 2002 e 2007) e trabalho impedido (CLOT, 2006) advindos das Ciências do Trabalho. No que se refere aos estudos das práticas discursivas, enfocou-se as contribuições de Bakhtin sobre dialogismo da linguagem (BAKHTIN, 1981 e 2003), a negação polêmica de Ducrot (1987) e o arcabouço teórico de Maingueneau (2001, 2002 e 2008) para os estudos enunciativos da Análise do Discurso. Os resultados nos possibilitaram apontar discursos circulantes subjacentes acerca do trabalho docente e refletir sobre tais construções de posições enunciativas que, em sua maioria, atribuem a responsabilidade pelos problemas no ensino ao professor. Além disso, identificamos contrastes entre os professores quanto à visão do ensino de Língua Portuguesa para o Ensino Fundamental

Beta and gamma vibrational bands in deformed nuclei

Energies and relative intensities of gamma transitions in ¹⁵²Sm, ¹⁵²Gd, ¹⁵⁴Gd, ¹⁶⁶Er, and ²³²U following radioactive decay have been measured with a Ge(Li) spectrometer. A peak fitting program has been developed to determine gamma ray energies and relative intensities with precision sufficient to give a meaningful test of nuclear models. Several previously unobserved gamma rays were placed in the nuclear level schemes. Particular attention has been paid to transitions from the beta and gamma vibrational bands, since the gamma ray branching ratios are sensitive tests of configuration mixing in the nuclear levels. As the reduced branching ratios depend on the multipolarity of the gamma transitions, experiments were performed to measure multipole mixing ratios for transitions from the gamma vibrational band. In ¹⁵⁴Gd, angular correlation experiments showed that transitions from the gamma band to the ground state band were predominantly electric quadrupole, in agreement with the rotational model. In ²³²U, the internal conversion spectrum has been studied with a Si(Li) spectrometer constructed for electron spectroscopy. The strength of electric monopole transitions and the multipolarity of some gamma transitions have been determined from the measured relative electron intensities.

The results of the experiments have been compared with the rotational model and several microscopic models. Relative B(E2) strengths for transitions from the gamma band in ²³²U and ¹⁶⁶Er are in good agreement with a single parameter band mixing model, with values of z₂= 0.025(10) and 0.046(2), respectively. Neither the beta nor the gamma band transition strengths in ¹⁵²Sm and ¹⁵⁴Gd can be accounted for by a single parameter theory, nor can agreement be found by considering the large mixing found between the beta and gamma bands. The relative B(E2) strength for transitions from the gamma band to the beta band in ²³²U is found to be five times greater than the strength to the ground state band, indicating collective transitions with strength approximately 15 single particle units.

Isotope shift studies in the rare earths and lead

Isotope shifts of K_α1 x-ray transitions were measured for the Neodymium isotopes Nd 142, 143, 144, 145, 146, 148 and 150, the Samarium isotopes Sm 147, 148, 149, 150, 152 and 154, the Gadolinium isotopes Gd 154, 155, 156, 157, 158 and 160, the Dysprosium isotopes Dy 162 and 164, the Erbium isotopes Er 166, 168 and 170, the Hafnium isotopes Hf 178 and 180 and the Lead isotopes Pb 204, 206, 207 and 208. A curved crystal Cauchois spectrometer was used. The analysis of the measurement furnished the variation of the mean square charge radius of the nucleus, δ˂r²˃, for 23 isotope pairs. The experimental results were compared with theoretical values from nuclear models. Combining the x-ray shifts and the optical shifts in Nd and Sm yielded the optical mass shifts. An anomaly was observed in the odd-even shifts when the optical and the x-ray shifts were plotted against each other.

稀土-β-二酮配合物的合成及其光谱性质的研究

以二苯甲酰甲烷（DBM）和2，2’-联二吡啶（BIPY）为配体，采用乙醇-水溶液析出法合成了三种稀土-β-二酮配合物：Gd（DBM）3BIPY、Sm（DBM）3BIPY、La（DBM）sBIPY。通过元素分析、MS、IR对配合物进行了表征，初步研究了这些配合物的紫外光谱性质。研究表明：配体DBM以烯醇式异构体与金属离子螯合，受螯合效应的影响，配体的IR、UV特征吸收峰均发生红移，染料在340nm-400nm近紫外区有强烈的电子吸收。

新型稀土-β-二酮配合物的合成与表征

以噻吩甲酰三氟丙酮（HTTA）和2，2-联二吡啶（BIPY）为配体，采用乙醇-水溶液析出法合成了稀土-β-二酮配合物Ln（TTA）3BIPY（Ln=Gd、Sm、La），其中La（TTA）3BIPY、Gd（TTA）3BIPY未见报道。通过元素分析、MS、IR、UV及热重分析对配合物进行了表征和分析，分析表明：配体HTTA以烯醇式异构体形式与金属离子相螯合，受螯合效应影响，配体的IR、UV特征吸收峰均发生红移，配合物在300～400nm近紫外区有强烈的电子吸收，起始分解温度高于250℃，失重迅速、显著。

Avaliação da customização por desgaste de pinos pré-fabricados de fibra de vidro

O objetivo deste estudo foi avaliar pinos pré-fabricados de fibra de vidro (White Post DC/FGM) submetidos à customização por desgaste da porção apical. Experimento 1: 5 pinos n. 4 foram divididos em 5 grupos (G) de acordo com o instrumento de desgaste: GA - sem desgaste, GB- mini torno industrial (Dentsply), GC - ponta diamantada n. 3195F (KG Sorensen), GD - disco de lixa de granulação média (Sof-Lex/3M/ESPE), GE- alicate (Tramontina). Observou-se a micromorfologia dos pinos em microscópio eletrônico de varredura (ZEISS/DSM 960). Experimento 2: 60 pinos de diferentes diâmetros foram divididos em 6 grupos: G0 - pinos n. 0,5, G1 - pinos n. 1, G2 - pinos n. 2, G3 - pinos n. 3, G4 - pinos n.4, G5 - pinos n. 4 com terço apical desgastado com discos de lixa até o equivalente ao terço apical dos pinos n. 2. Os pinos foram submetidos ao teste de flexão de 3 pontos na máquina de ensaios universal (Instron 5500 R), conforme ISO 10477. Experimento 3: 20 caninos humanos permanentes sofreram tratamento endodôntico e remoção das coroas clínicas padronizando 15 mm de remanescente radicular. Os dentes foram incluídos em resina acrílica com simulação do ligamento periodontal, receberam férula de 2 mm e foram divididos em 2 grupos: GI - pinos n. 4 cimentados em condutos preparados com broca equivalente ao pino (FGM), GII - pinos n. 4 customizados no terço apical cimentados em condutos preparados com brocas (FGM) equivalentes aos pinos n. 2 em 10 mm e n. 4 em 5 mm. Os pinos foram cimentados com cimento resinoso (Rely X U100/3M/ESPE), os corpos de prova receberam coroas diretas de resina composta (Enforce Core/Dentsply) padronizadas com coras de policarbonato (TDV) e foram submetidos ao teste de resistência à fratura na Instron a 45da ferramenta cilíndrica, com força de 500 N aplicada a 2 mm da incisal na face palatina/lingual, com velocidade de 0,5 mm/min até falha. O padrão de fratura foi classificado em favorável ou desfavorável. Os resultados foram tratados estatisticamente por teste de análise de variância (ANOVA, p<0,05). Os resultados dos testes de flexão e fratura foram respectivamente: G0 - 58,406,40; G1 - 83,959,43; G2- 103,4219,17; G3 - 160,7817,30; G4 - 170,4711,28; G5 - 106,3521,96; GI - 303,0262,21 e GII - 402,81131,97. O padrão de fratura foi tratado por Mann-Whitney que observou semelhança estatística entre os grupos. Concluiu-se que o desgaste de pinos de fibra de vidro com pontas diamantadas ou discos de lixa produz alterações micromorfológicas aceitáveis. O corte com alicate deve ser evitado. A customização por desgaste da porção apical de pinos de fibra de vidro diminui a resistência à flexão a valores aceitáveis. Dentes restaurados com pinos de fibra de vidro customizados por desgaste possuem resistência à fratura superior a dentes restaurados com pinos intactos. A customização por desgaste facilita a adaptação do pino ao conduto radicular e preserva a estrutura dental.

X 射线转换屏用Tb3+激活磷酸盐发光玻璃

Phosphate glasses 60P2O5-15CS2O- 15Al2O3-10BaO were made by high temperature melt-annealing method. The absorption spectra, excitation spectra and emission spectra of Gd³⁺-Tb³⁺ and Ce3+-Gd³⁺-Tb³⁺ co-doped phosphate glass 60P2O5-15CS2O- 15Al2O3-10BaO were studied. The experimental results indicate that, the doping of Ce3+ and Gd³⁺ in Tb³⁺ phosphate glass has a good effect on the 545 nm emission of Tb³⁺ at UV excitation. The Ce3+-Gd³⁺-Tb³⁺ co-doped phosphate glass have a good x-ray luminescence at the radiation of x-ray with energy in 50-120 kev, and a high space resolution. The Ce3+-Gd³⁺-Tb³⁺ co-doped phosphate luminescence glass is a promising material for using in the digital radiography system in medical devices.

Avaliação dos efeitos da hiperglicemia sobre a estrutura vascular peniana em coelhos Nova Zelândia

Pacientes com diabetes mellitus (DM) têm elevadas taxas de disfunção erétil (ED). Diversos estudos examinaram esta associação. A associação entre o processo de hipertrofia vascular diabética e o grau de comprometimento dos seios cavernosos é pouco estudada. A proposta do presente estudo foi avaliar a estrutura vascular do tecido erétil de coelhos diabéticos e coelhos normais, através de histomorfometria computadorizada da artéria dorsal do pênis e dos seios vasculares cavernosos em ambos os grupos. Foram utilizados 20 coelhos adultos machos da raça Nova Zelândia, divididos em dois grupos com 10 animais cada, o grupo diabético (GD) e o grupo controle (GC). Os animais foram previamente anestesiados e os coelhos do grupo GD receberam aloxano na dose de 100mg/kg, via endovenosa para indução da diabetes. Após 10 semanas, os animais foram mortos e os pênis retirados. Fragmentos do pênis foram fixados em formalina tamponada durante 24-48 horas e processados para parafina. Para análise imunohistoquímica e identificação das fibras musculares lisas, foi utilizado o anticorpo anti alfa-actina. Foram feitas análises da espessura média das túnicas íntima e média da parede da artéria dorsal do pênis (ADP), densidade nuclear na túnica média e avaliação por microscopia de polarização do conteúdo colágeno na túnica adventícia. Na túnica íntima foram observadas vacuolizações no endotélio. Os valores encontrados para espessura de GC e GD foram respectivamente (em m): 35,0123,177 e 44,3308,434 (P=0,0350). Foi encontrada diferença na área média da parede da ADP (P=0,0179). Para densidade nuclear GC 0,0071540,001954 núcleos/μm e GD 0,0048080,002069 núcleos/μm (P=0,0855). Foram observadas mudanças na birrefringência das fibras colágenas na túnica adventícia, passando de alaranjado no grupo GC para esverdeado no grupo GD, indicando a mudança em sua espessura. A área ocupada pelos seios cavernosos apresentou diminuição significativa de 37 % no grupo diabético (P=0,0013). Este conjunto de alterações sugere que a hiperglicemia crônica provocada pelo diabetes levou a um processo de hipertrofia da musculatura lisa na parede vascular e nas trabéculas do corpo cavernoso, com diminuição da área dos seios, o que possivelmente altera as propriedades hemodinâmicas do órgão

LD抽运Yb:GSO实现1090nm低阈值激光运转

We report what we believe to be the first demonstration of laser operation with a novel laser material of Yb3(+) -doped Gd-2 SiO2 (Yb: GSO) pumped by a laser diode at 940 nm. We obtained a low lasing threshold of 1.27 kW/cm(2) with the center wavelength of 1090 nm, which is lower than the value of 1.53 kW/cm(2) predicted for Yb: YAG. The maximal output power of 360 mW was obtained with a 2% output, which corresponds to a slope efficiency up to 19%.