Ta含量对NiCoCrAlY涂层性能的影响

采用真空雾化的方法制备了Ta含量为0、2%及5%的NiCoCrAlYTa合金粉末,利用超音速火焰喷涂制备了三种涂层,研究了Ta对合金粉末微观组织及物相的影响,绘制了1050℃条件下涂层的高温氧化动力学曲线,研究了500h氧化试验后涂层组织和β相的分布,初步探讨了Ta元素对改善涂层抗氧化性能的作用机理。研究结果表明:Ta通过提高MCrAlY体系抗氧化元素的溶质浓度,促进了氧化膜的形成,随着Ta含量的增加,涂层的内氧化程度降低,涂层抗氧化性能提高。但含Ta涂层在长时间氧化条件下会生成CrTaO_4、AlTaO_4等尖晶石类氧化物,且Ta的氧化物PBR值较大,对涂层的抗热震性能不利。     

A dinuclear iron complex as a precatalyst for water oxidation under alkaline conditions

Water oxidation is a key reaction for water splitting. The decomposition of Fe-based-molecular structures toward Fe-based oxides is a promising method for oxygen-evolution reaction (OER) through water oxidation. The decomposition of Fe-based-molecular structures method results in a slow decomposition of precatalysts and forms Fe oxide-based catalysts. In this study, the Fe species formed through the decomposition of a dinuclear Fe(III) complex under OER is investigated by X-ray photoelectron spectroscopy, scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, and the electrochemical method. In addition, using Ni(OH)₂, a new approach is reported for detecting trace Fe species on the electrode surface. The resulting Fe oxide-based catalyst shows a catalytic current with an onset of 621 mV overpotential and the Tafel slope of 113.7 mV/decade at pH 11 in a buffer phosphate.     

Excision of Oxidatively Generated Guanine Lesions by Competitive DNA Repair Pathways

The base and nucleotide excision repair pathways (BER and NER, respectively) are two major mechanisms that remove DNA lesions formed by the reactions of genotoxic intermediates with cellular DNA. It is generally believed that small non-bulky oxidatively generated DNA base modifications are removed by BER pathways, whereas DNA helix-distorting bulky lesions derived from the attack of chemical carcinogens or UV irradiation are repaired by the NER machinery. However, existing and growing experimental evidence indicates that oxidatively generated DNA lesions can be repaired by competitive BER and NER pathways in human cell extracts and intact human cells. Here, we focus on the interplay and competition of BER and NER pathways in excising oxidatively generated guanine lesions site-specifically positioned in plasmid DNA templates constructed by a gapped-vector technology. These experiments demonstrate a significant enhancement of the NER yields in covalently closed circular DNA plasmids (relative to the same, but linearized form of the same plasmid) harboring certain oxidatively generated guanine lesions. The interplay between the BER and NER pathways that remove oxidatively generated guanine lesions are reviewed and discussed in terms of competitive binding of the BER proteins and the DNA damage-sensing NER factor XPC-RAD23B to these lesions.     

Simulation studies on a rotating ring disk electrode: Effects of ionic migration with kinetic complication-disk results

In continuation to my previous work (Guha S. AIChE J. 2013;59(4):1390-1399), in this work, effects of ionic migration are evaluated for disk region of a rotating ring disk electrode system by numerically solving complex differential equations, developed for mass transfer along with kinetic complication in presence of ionic migration under limiting current condition. The system for simulation is 0.01 M Fe₂(SO₄)₃ solution with H₂SO₄ as supporting electrolyte. Simulation cases are presence and absence of ionic migration with kinetic complication (oxidation of Fe²⁺ to Fe³⁺ under O₂ pressure). Results show that concentration boundary layer thickness of reactant Fe³⁺ reduces appreciably and steady-state disk current reduces substantially in presence of migration. Simulated steady-state disk current in absence of migration case agrees well with published data. Results indicate higher Fe²⁺ concentration in presence of migration and thereby higher rate of oxidation of Fe²⁺ to Fe³⁺ at all rate constant values.     

A dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanopaticles showing significant electrocatalytic activity towards ethanol oxidation reaction (EOR)

To the best of our knowledge, this is the first time to report the preparation of a dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanoparticles (denoted as Pd_xNi_y NPs) via a hydrothermal method using NU and PdO·H₂O as the starting materials. The samples prepared at the mass ratio of NU to PdO·H₂O 1:1, 1:2 and 2:1 were, respectively, nominated as catalyst c₁, c₂ and c₃. The chemical compositions of all synthesized catalysts were mainly studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), revealing that metallic Ni was one main component of all prepared catalysts. Surprisingly, the main diffraction peaks appearing in the XRD patterns of all prepared catalysts were assigned to the metallic Ni rather than the metallic Pd. Very interestingly, as indicated by the TEM images, a large number of dotted nanowires arrayed by numerous equidistant 5 nm sized nanoparticles were distinctly exhibited in catalyst c₁. More importantly, when being used as electrocatalysts for EOR, all prepared catalysts exhibited an evident electrocatalytic activity towards EOR. In the cyclic voltammetry (CV) test, the peak current density of the forward peak of EOR on catalyst c₁ measured at 50 mV s^?1 was as high as 56.1 mA cm^?2, being almost 9 times higher than that of EOR on catalyst c₃ (6.3 mA cm^?2). Particularly, the polarized current density of EOR on catalyst c₁ at 3600 s, as indicated by the chronoamperometry (CA) experiment, was still maintained to be around 1.47 mA cm^?2, a value higher than the latest reported data of 1.3 mA cm^?2 (measured on the pure Pd/C electrode). Presenting a novel method to prepare dotted nanowires arranged by 5 nm sized nanoparticles and showing the significant eletrocatalytic activities of the newly prepared dotted nanowires towards EOR were the major contributions of this preliminary work.     

Recent advances in two-dimensional Pt based electrocatalysts for methanol oxidation reaction

Direct methanol fuel cells (DMFCs) had been attracted considerable attention for its advantages of high energy density, simplified systems and readily transportation and storage of methanol. However, the notoriously sluggish kinetics of methanol oxidation reaction (MOR) of the anode reaction, had greatly affected the commercialization of DMFCs. On one hand, Pt based catalyst are still the most effective MOR catalysts, while the high cost caused by the high loadings of electrocatalyst to compensate the low MOR activity impedes the wide accessible of DMFCs. In addition, the occurrence of catalyst poisoning owing to the strong interaction between Pt and carbon monoxide (CO) generated during the MOR processing, further leading to the fast decay in the performance and stability of MOR electrocatalysts. Two-dimensional (2D) Pt based nanostructures is regarded to be one promising and effective class of MOR electrocatalysts, and attracted much attention due to the high electron mobility, highly exposed active sites, and extraordinary thermal conduction. In this review, the mechanism of MOR was firstly introduced, and then the synthesis conditions, structure characteristics and methanol oxidation performances both in acidic and alkaline dielectric of 2D Pt based nanocatalysts were introduced. Subsequently, we briefly analyzed the structural characteristics of 2D Pt based nanocatalysts and their advantages, including the low platinum loadings, high specific surface area and majority of atomic active sites exposed. Finally, the opportunities and challenges for designing of advanced 2D Pt based nanocatalysts was proposed and discussed.     

A straightforward one-pot synthesis of Pd–Ag supported on activated carbon as a robust catalyst toward ethanol electrooxidation

Direct Ethanol Fuel Cells (DEFCs) have fascinated remarkable attention on account of their high current density and being environmentally friendly. Developing efficient and durable catalysts with a simple and fast method is a great challenge in the practical applications of DEFCs. To this end, the bimetallic Pd–Ag with adjustable Pd:Ag ratios were synthesized via a simple and one-pot strategy on activated carbon as a support in this study. The Pd–Ag/C catalysts with different molar ratios were synthesized by simultaneous reduction of Pd and Ag ions in the presence of the ethanolic sodium hydroxide as a green reducing agent for the first time. Several different methods, including FE-SEM, HR-TEM, XRD, XPS EDX, ICP-OES, and BET were used to confirm the structure and morphology of the catalysts. The performance of catalysts was also examined in ethanol oxidation. Obtained results of electrochemical experiments revealed that the Pd₃–Ag₁/C catalyst had superior catalytic activity (2911.98 mAmg^?1_Pd), durability, and long-stability compared to the other catalysts. The excellent catalytic characteristic can be attributed to the synergistic effect between Pd and Ag. We presume that our simple method have the chance to be utilized as a proper method for the synthesis of fuel cell catalysts.     

On the dependence of interfacial resistance on contact materials between cathode and interconnect in solid oxide fuel cells

The dependence of interfacial contact resistance (ICR) on contact materials between cathode and interconnect is systematically studied under both isothermal oxidation and thermal cycling conditions. Three kinds of cathode current-collecting layer (CCCL) are used, (La,Sr) (Co,Fe)O₃ (LSCF), LSCF+10%Ag, and Ag, and tested in a SUS430/CCCL/SUS430 sandwich structure to simulate the actual operation of the solid oxide fuel cells (SOFCs). Experimental results show that the ICR of LSCF+10%Ag exhibits the smallest value, in comparison with the specimens with LSCF and Ag paste, as well as the sample without a CCCL. For LSCF+10%Ag contact, the ICR increases from 0.0069 mΩ cm² to 3.74 mΩ cm² under an isothermal condition for 150 h, then increases from 3.74 mΩ cm² to 10.79 mΩ cm² after 15 thermal cycles. This work provides information for the understanding of possible mechanisms of performance degradation of SOFCs.