Role of a low level of La2O3 dopant on the tetragonal-to-monoclinic phase transformation of ceria-yttria co-stabilized zirconia

Yttria, yttria-ceria and yttria-ceria-lanthana stabilized zirconia powders were prepared by coprecipitation. Their tetragonal-to-monoclinic phase (t→m) transformation was investigated by calcining the powders in a temperature range of 400–1400 °C for 2 h. The results show that after doping with 0.1 to 0.3 mol.% La₂O₃ and calcining at 1400 °C in air, unusual redox behaviours of cerium were detected in the 1.5 mol.% Y₂O₃+5.5 mol.% CeO₂ co-stabilized zirconia. Grain refinement and a sharp reduction in oxygen vacancy concentration were observed simultaneously. The t→m transition was not found in the 0.1 mol.% La₂O₃ doped zirconia but appeared in the cases with a higher dopant content. The changes are discussed with regards to the grain size, valence change of cerium, presence of oxygen vacancies, and segregation of the dopants at grain boundaries.     

Efficient hydrogen evolution by liquid phase plasma irradiation over Sn doped ZnO/CNTs photocatalyst

In this study, the liquid phase plasma (LPP) was irradiated over pure zinc oxide (ZnO), strontium (Sn) doped ZnO, and Sn doped ZnO/CNTs photocatalysts for hydrogen evolution from pure water and from aqueous solution of water-methanol. The possible relationship between hydrogen evolution and optical emissions from LPP for activation of ZnO based photocatalysts was revealed. The role of carbon nanotubes (CNTs) as a support material for improved photocatalytic hydrogen evolution was also investigated in this study. The photocatalytic hydrogen evolution from water mixed methanol under LPP irradiation was compared with pure water splitting. The photolysis produced negligible amount of hydrogen due to minimal photodecomposition of water molecules under LPP irradiation. The plasma born reactive species also played crucial role in photolysis. However, the hydrogen evolution rate increased significantly in the presence of ZnO photocatalyst. Further improvement in hydrogen evolution rate was noticed on Sn doping of ZnO and compositing with CNTs. The highest hydrogen evolution rate of 11.46 mmh⁻¹g⁻¹ from water mixed methanol was achieved with Sn doped ZnO/CNTs photocatalyst. This hydrogen evolution rate from water-methanol solution was 9 times higher than from the splitting of pure water. This hydrogen evolution rate is attributed to excessive production of hydroxyl radicals, red shift in optical band gap of Sn doped ZnO/CNTs photocatalyst, slow electron-hole recombination and fast decomposition of methanol as sacrificial reagent.     

Contributions of oxygen vacancies to the hydrogen evolution catalytic activity of tungsten oxides

The tungsten trioxide attracts less attention due to the low electron transfer kinetics that hinders the interaction of electrons and ions during the hydrogen evolution reaction (HER). But the oxygen vacancy strategy can inspire its electrocatalytic activity for HER because it has a positive effect on improving the charge transfer and compensating for the weak hydrogen adsorption of the tungsten trioxide. By synthesizing a series of substoichiometric tungsten oxides, we reveal the linear relationship between the catalytic activity and the content of oxygen vacancies, which indicates that the oxygen vacancy strategy is an achievable route to enhance the HER for metal oxides.     

Carbon supported nickel phosphide as efficient electrocatalyst for hydrogen and oxygen evolution reactions

Hydrogen production through water splitting is an efficient and green technology for fulfilling future energy demands. Carbon nanotubes (CNT) supported Ni₂P has been synthesized through a simpler hydrothermal method. Ni₂P/CNT has been employed as efficient electrocatalysts for hydrogen and oxygen evolution reactions in acidic and alkaline media respectively. The electrocatalyst has exhibited low overpotential of 137 and 360 mV for hydrogen and oxygen evolution reactions respectively at 10 mA cm^?2. Lower Tafel slopes, improved electrochemical active surface area, enhanced stability have also been observed. Advantages of carbon support in terms of activity and stability have been described by comparing with unsupported electrocatalyst.     

Promoted electrocatalytic hydrogen evolution performance by constructing Ni12P5–Ni2P heterointerfaces

Transition metal phosphides (TMPs) have been considered as cheap alternatives of precious metal platinum for electrochemical hydrogen evolution reaction (HER). In the past decades, many reports have indicated that the engineering of heterointerfaces between different components could efficiently enhance the activity of HER catalysts. Here, we report a facile method to construct Ni₁₂P₅–Ni₂P heterostructure by using a low temperature phosphorization strategy. The obtained Ni₁₂P₅–Ni₂P heterostructure shows high activity toward HER with an overpotential value of 166 mV at 10 mA cm^?2 and a Tafel slope of 60 mV dec^?1 in 0.5 M H₂SO₄. Compared with pure Ni₂P and Ni₁₂P₅, the Ni₁₂P₅–Ni₂P heterostructure has more active sites and faster HER kinetics due to the presence of the interfaces between Ni₁₂P₅ and Ni₂P. Furthermore, we used the obtained Ni₁₂P₅–Ni₂P as cathodic catalyst and IrO₂/Ti as anodic material to set up a proton exchange membrane (PEM) electrolyzer which shows good stability after 120 h continuous constant current electrolysis at 200 mA cm^?2. This work demonstrates the positive effect of heterostructure for HER catalysts and provides a feasible strategy for constructing earth-abundant electrocatalysts.     

一种基于GN算法的动态图划分方法

随着图规模的急剧增长，对动态图进行实时处理的需求日益增加。大多现有的算法针对静态图划分是有效的，直接用其处理动态图会带来较大的通信开销。针对该问题，提出一种基于GN算法的动态图划分方法。首先收集一段时间内加入动态图中的顶点；然后，利用GN算法对这些新加入的顶点进行预划分，产生若干个内部联系紧密的社区；最后，将预划分产生的社区结果插入到已经划分好的当前图中。实验从交叉边数和负载均衡度两方面将该方法与传统流式划分方法进行比较，结果表明， 在公开数据集上，该方法的交叉边数降低了13%，负载均衡度减少了42.3%。由此可见，该方法的划分质量明显优于传统的流式划分方法。     

Evolution of core–rim structures and phase transformations in infra-red transmitting Y-α-SiAlON ceramics

Core–rim structures were observed as common features in Y-α-SiAlON ceramics hot-pressed between 1550?1950 °C. We found most dopants were taken into α’-rims, and a transition layer grown first on α-cores from liquid-phase over-saturated with metal solutes. Elongated β’-grain were formed as minor phase with α’- or AlN-cores thus only after the α’ matrix had consumed up all Y solutes, revealing that the α’ → β’ transformation is controlled by the transient liquid-phase and similar defects and dangling bonds could be detected in both SiAlON phases by cathodoluminescence. Quantitative assessment of Y_m/3Si_12?(m+n)Al_m+nO_nN_16?n demonstrates the multiphase evolution, initiated by over-saturation of Y solutes at low temperatures thus retaining α-phase as cores to lower the infra-red transmittance, dictated by homogenization of Al solutes at higher temperature. The elimination of those phase boundaries leads to better dopant and sintering design for achieving transparent and high-performance SiAlON ceramics.     

Effects of TGO growth on the stress distribution and evolution of three-dimensional cylindrical thermal barrier coatings based on finite element simulations

Based on the ultrasonic C-scan results of 8YSZ coatings after thermal cycles, three-dimensional cylindrical numerical simulations of the physical geometry model of the thermal barrier coating (TBC) sinusoidal surfaces were conducted with finite elements to estimate the stress distribution and evolution law of the top coat (TC)/bond coat (BC) interface, including the centre and edge of the specimen affected by the dynamic growth of the thermally grown oxide (TGO). The results show that when a layer of TGO is grown on the TC/BC interface, compressive stress is uniformly distributed on the TGO interface, and the stress value decreases as a function of the TGO layer thickness. When the thickness of the TGO exceeds a certain value, the compressive stress of all parts of the interface gradually changes to tensile stress; meanwhile, the edges of the model affected by the crest and trough effects of the wave are reflected in the radial and circumferential directions, especially along the axial direction, with alternating concentrated tensile and compressive stresses. TGO growth imposes a minor influence on the magnitude and distributions of the radial and circumferential stresses at the BC interface. The linear elasticity, creep, fatigue, and stress accumulation effects of each layer of TBCs in each thermal cycle were fully considered in this model. The model not only interprets the crest and trough effects of the TC/BC surface interface during the growth of TGO, but also interprets the effects of the core and edge of the cylindrical model, further revealing the reason for which the core and edge of the TBC will most likely form cracks.     

Evolution of the structure and chemical composition of the interface between multi-component silicate glasses and yttria-stabilized zirconia after 40,000 h exposure in air at 800 °C

The chemical and structural stability of two commercial multicomponent silicate glasses (SCN and G6) in contact with yttria-stabilized zirconia (YSZ) was investigated after exposure times of up to 40,000 h in air at 800 °C. With exposure time, interfacial layers develop at the SCN-YSZ and G6-YSZ interfaces, which were characterized in detail using both quantitative chemical analysis and atomic-resolution imaging. At the SCN-YSZ interface, a Ca-Ba-Si-O reaction phase was found to grow by diffusion control. In G6-YSZ, Raman spectroscopy and electron microscopy revealed a disorganized interfacial reaction later between G6 and YSZ, and the occurrence of cubic to tetragonal to monoclinic phase transformations in YSZ. This microstructural evolution is discussed in terms of devitrification resistance of glass and diffusion processes at interfaces.     

High temperature oxidation behavior of MoSi2–Al2O3 composite coating on TZM alloy

A novel MoSi₂–Al₂O₃ composite coating was prepared on Mo-based TZM alloy by slurry sintering method. The oxidation behavior of the coating was evaluated at 1600 °C in static air. Microstructure and phase composition of the as-prepared and oxidized coatings were characterized, and the antioxidant mechanism of the coating at high temperature was discussed. A three-layer structure was observed in the as-prepared coating, consisting of a ～2 μm thick Mo₅Si₃ diffusion layer, a ～65 μm thick MoSi₂ inner layer and a ～36 μm thick outer layer of mixture of MoSi₂ and Al₂O₃. After oxidation at 1600 °C for 5 h, all MoSi₂ phases were completely converted to intermediate silicide Mo₅Si₃ by solid-state diffusion, and the formed Mo₅Si₃ phase would be transformed into Mo₃Si phase with further extending the oxidation time. Furthermore, a dense oxide layer of SiO₂-mullite was formed on the specimen surface, which can effectively protect the material to further oxidation. The MoSi₂–Al₂O₃ coating could protect the substrate effectively at 1600 °C for 20 h without failure. The enhanced oxidation resistance of MoSi₂–Al₂O₃ coating is due to the formation of multi-layer structure containing a SiO₂-mullite composite oxide outer layer with high thermal stability and low oxygen permeability.