Combining molybdenum carbide with ceria overlayers to boost Mo/CeO2 catalyzed ammonia synthesis

The design of an efficient non-noble metal catalyst is of burgeoning interest for ammonia synthesis. Herein, we report a Mo₂C/CeO₂ catalyst that is superior in ammonia synthesis activity. In this catalyst, molybdenum carbide coexisted with the ceria overlayers which is from the ceria support as the strong metal–support interaction. There is a high proportion of low-valent Mo species, as well as high concentration of Ce³⁺ and surface oxygen species. The presence of Mo₂C and CeO₂ overlayers not only leads to enhancement of hydrogen and nitrogen adsorption, but also facilitates the desorption and exchange of adsorbed species with the gaseous reagents. Compared with the Mo/CeO₂ catalyst prepared without carbonization, the Mo₂C/CeO₂ catalyst is more than sevenfold higher in ammonia synthesis rate. This work not only presents an explicit example of designing Mo-based catalyst that is highly efficient for ammonia synthesis by tuning the adsorption and desorption properties of the reactant gases, but opens a perspective for other elements in ammonia synthesis.     

Study of haze emission efficiency based on new co-opetition data envelopment analysis

As haze intensifies in China, controlling haze emission has become the country's top priority for environmental protection. Because haze moves across different regions, it is necessary to develop a data envelopment analysis (DEA) model underpinned by both competition and cooperation to evaluate the haze emission efficiency in different provinces. This study innovatively adopts the spatial econometrics to construct the co-opetition matrices of Chinese provinces, then builds the co-opetition DEA model to evaluate the haze emission efficiency of them, and finally uses the haze data of 2015 as an example to assess the applicability of the model. The results of the study include the following: First, compared with the traditional CCR (A. Charnes & W. W. Cooper & E. Rhodes) model, this study constructs the co-opetition DEA cross-efficiency model that integrates haze's feature of cross-border moving; thus, it is more in line with the reality of haze emission and movement. Second, compared with the efficiency value gained from the CCR model, the haze emission efficiency values for Tianjin and Guangdong, two decision-making units, register greater variance when using the DEA model. The reason might lie in that they have a different spatial transportation relationship with their surrounding provinces. Third, the haze emission efficiency of provinces, according to the evaluation based on the co-opetition DEA method, varies greatly: Those with high efficiency are mostly inland provinces with slow economic growth and adverse climatic conditions, whereas many of the provinces with low efficiency are located in the relatively prosperous East China. The specific co-opetition DEA model constructed in this study enriches the research on the DEA model, which can be applied to the emission efficiency evaluation of similar pollutants around the world and can contribute empirical support to the haze reducing efforts of the government with its empirical results.     

Wear mechanism of a novel AlSiMgAl2O4Al2O3 composite used in the low vessel of an RH secondary refining furnace

A novel AlSiMgAl₂O₄Al₂O₃ composite brick was prepared and evaluated in the low vessel of an RH (the initials of Ruhrstahl and Hereaeus) secondary refining furnace; it was characterized by X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. The results show that after use, the AlSiMgAl₂O₄Al₂O₃ composite has a functional gradient with an erosion zone–reinforced zone–original zone phase distribution, in which the phases in the erosion zone (0–1.8?cm) are a Mg-hercynite spinel solid solution, α-Al₂O₃, and minor amount of Al₃Fe₅O₁₂. Furthermore, the phases in the reinforced zone (1.8–5.0?cm) are γ-AlON, 21RSiAlON, SiC, Mg_0.388Al_2.408O₄, and α-Al₂O₃; i.e., the Al and Si in the composite are completely converted into non-oxide reinforced phases. Finally, the phases in the original zone (>5.0?cm) show no change. The reaction mechanism is as follows. During operation, a Mg-hercynite spinel solid solution is formed in the erosion zone due to a reaction between MgAl₂O₄ and FeO from a refinery operation. Therefore, the slag erosion of the material is improved. The Al and Si metals undergo active oxidation, and 21RSiAlON flakes are subsequently formed from the products of the metastable Al₂O(g), SiO(g), and N₂(g) in the ambient. The γ-AlON is formed by a carbothermal reduction nitridation of the α-Al₂O₃ and residual active carbon from the resin binder. The 21RSiAlON and γ-AlON reinforce the composite brick and improve its high temperature performance accordingly. Its service life is 110% that of the magnesia-chrome bricks used in the same period. The reaction model was also established.     

Lead-free sodium niobate nanowires with strong piezo-catalysis for dye wastewater degradation

In this work, the hydrothermally-synthesized sodium niobate nanowires were used to decompose Rhodamine B dye solution through the piezo-catalytic effect. With the sodium niobate catalyst, a high piezo-catalytic degradation ratio of ～80% was achieved under the excitation of vibration for the Rhodamine B dye solution (～5?mg/l). These active species in the catalytic process, hydroxyl radicals and superoxide radicals with the strong oxidation ability, were also observed, which confirmed the key role of piezoelectric effect for piezo-catalysis. The piezo-catalysis of sodium niobate nanowires provides a high-efficiency and reusable tool in application in depredating the dye wastewater.     

Oxide-Scale Evolution on a New Ni–Fe-Based Superalloy at High Temperature

Oxidation of Metals - The isothermal oxidation behavior and oxide-scale evolution on a newly developed Ni–Fe-based superalloy were investigated. Three oxidation stages were generally...     

Filtered adaptive constrained sampled-data control for uncertain multivariable nonlinear systems

A filtered adaptive constrained sampled-data controller for uncertain multivariable nonlinear systems in the presence of various constraints is synthesized in this paper. A piecewise constant adaptive law drives that estimation error dynamics to zero at each sampling time instant yields adaptive parameters. The filtered control scheme consists of two components. Based on an estimation/cancellation strategy, a disturbance rejection control law is designed to compensate the nonlinear uncertainties within the bandwidth of low-pass filters, whereas a constraint violation avoidance control law is designed to solve an online constrained optimization problem. Although a reduced sampling time helps to minimize the estimation error caused by the neglect of unknowns, the resulting aggressive signals put more restrictions on the control law. Greater sacrifice of tracking performance is required to satisfy the constraints. The constraints violation avoidance control law is in favor of a larger sampling time. Sufficient conditions are given to guarantee the stability of the closed-loop system with the sampled-data controller, where the input/output signals are held constant over the sampling period. Numerical examples are provided to validate the theoretical results, comparisons between the constrained sampled-data controller and unconstrained adaptive controller with the implementation of different sampling times are carried out.     

Fabrication of dense nano-laminated tungsten carbide materials doped with Cr3C2/VC through two-step sintering

This work investigates the critical roles of two-step sintering (TSS) and laminated structure on the sintering behavior and mechanical properties of functionally graded WC-TiC-Al₂O₃ nanostructured composite materials doped with Cr₃C₂/VC. Results show that excellent mechanical properties are achieved for tailored TSS conditions with a hardness of 27.91?±?2.3?GPa and a flexural strength of 1423.3?±?23.5?MPa. The desirable mechanical properties are attributed to the suppressed grain growth without densification deterioration. TSS is more effective in facilitating the favorable dispersion of secondary phase toughening nano-particulates in a WC matrix than conventional sintering (CS). Cr₃C₂/VC dopant plays an important role in maximizing and shifting the temperature range of the kinetic window for WC-Al₂O₃ composites. Al₂O₃ crack deflection, transgranular Al₂O₃, microcracking, WC crack bridging and plate-like WC crack deflection are the major toughening mechanisms. Residual surface compressive stress induced by the graded structure is also an appreciated contribution to the improvement of mechanical properties.     

Transparent niobate glass-ceramics for optical limiting

The construction of nonlinear optical materials featuring asymmetric transmission of light is of great technological importance for various applications, including optical switching and optical power limiting. A significant challenge is the scalable fabrication of material candidates with good photochemical stability, high optical transmittance, and excellent optical limiting performance. Here, we present a nanocrystallization avenue for constructing hybrid optical limiting materials that exhibit ultrafast and robust optical limiting performance. The experimental results show that the controllable relaxation of a niobate glass may lead to the clustering of Nb-O units and contracting of the bandgap. It results in the notable improvement in nonlinear optical properties, including the enhanced saturation irradiance (380 GW/cm²), doubly increased nonlinear coefficient, and decreased limiting threshold (200 GW/cm²). Our results suggest a promising material that exhibits promising applications for protecting eyes and sensitive components from laser-induced damage.