Wavelength-dependent photoactivity of ZnxCd1−xS and ZnCo2O4/ZnxCd1−xS for H2 and H2O2 production

Zinc cadmium sulfide (Zn_xCd_1?xS) is a good photocatalyst for hydrogen evolution reaction (HER), but an optimum x (x_m) at which a maximum HER rate is reached varies from one report to another. In this work, we examine the effect of light wavelength, not only for the HER to H₂ in the presence of Na₂S and Na₂SO₃, but also for oxygen reduction reaction (ORR) without addition of any sacrifices. For the HER under a 365 and 420 nm LED lamp, the x_m were 0.9 and 0.7, respectively. For the HER under a 330 and 395–515 nm cut-off xenon lamp, the x_m were 0.7 and 0.5, respectively. For the ORR under a 420 nm cut-off halogen lamp, a maximum production of H₂O₂ was observed at x = 0.3. Furthermore, after 4% ZnCo₂O₄ loading, Zn_xCd_1?xS had an increased activity and stability, either for the HER or for the ORR. Through a (photo)electrochemical measurement, it is proposed that the photocatalytic activity of Zn_xCd_1?xS is determined by its light absorptivity and electron reactivity. The improved performance of n-type Zn_xCd_1?xS by p-type ZnCo₂O₄ is due to formation of a p-n junction, promoting the HER (ORR) on Zn_xCd_1?xS, and the sulfide (water) oxidation on ZnCo₂O₄. This work highlights that Zn_xCd_1-xS is a promising photocatalyst for H₂ and H₂O₂ production, respectively.     

Thermal and photon effects on the reaction of H2 and O2 to water over Ag–Pd/TiO2

The reaction of H₂ and O₂ to water are studied over a Ag–Pd/TiO₂ anatase catalyst, under dark and photo-irradiation conditions in the gas and liquid phases. The catalyst consisted of metal particles of mean size of ca.1 nm dispersed over 10–15 nm TiO₂ particles. Kinetic parameters including order of reaction (n), rate constant (k), and activation energy (E_a), were evaluated. E_a for the thermal reaction was found to be 49-47 kJ mol^?1. The oxidation reaction rate constant was found to be ca. 3 times higher in the presence of photons when compared to dark reaction at room temperature. The overall quantum yield of the reaction in the slurry phase was found to be 0.09. Considering the number of metal particles on TiO₂, the photon yield per metal particle was found to be 0.16. A possible explanation of the changes in kinetics with respect to experimental conditions is given.     

Ru-doped 3D porous Ni3N sphere as efficient Bi-functional electrocatalysts toward urea assisted water-splitting

Developing efficient, stable and ideal urea oxide (UOR) electrocatalyst is key to produce green hydrogen in an economical way. Herein, Ru doped three dimensional (3D) porous Ni₃N spheres, with tannic acid (TA) and urea as the carbon and nitrogen resources, is synthesized via hydrothermal and low-temperature treated process (Ru–Ni₃N@NC). The porous nanostructure of Ni₃N and the nickel foam provide abundant active sites and channel during catalytic process. Moreover, Ru doping and rich defects favor to boost the reaction kinetics by optimizing the adsorption/desorption or dissociation of intermediates and reactants. The above advantages enable Ru–Ni₃N@NC to have good bifunctional catalytic performance in alkaline media. Only 43 and 270 mV overpotentials are required for hydrogen evolution (HER) and oxygen evolution (OER) reactions to drive a current of 10 mA cm^?2. Moreover, it also showed good electrocatalytic performance in neutral and alkaline seawater electrolytes for HER with 134 mV to drive 10 mA cm^?2 and 83 mV to drive 100 mA cm^?2, respectively. Remarkably, the as-designed Ru–Ni₃N@NC also owns extraordinary catalytic activity and stability toward UOR. Moreover, using the synthesized Ru–Ni₃N@NC nanomaterial as the anode and cathode of urea assisted water decomposition, a small potential of 1.41 V was required to reach 10 mA cm^?2. It can also be powered by sustainable energy sources such as wind, solar and thermal energies. In order to make better use of the earth's abundant resources, this work provides a new way to develop multi-functional green electrocatalysts.     

Effects of multiple freeze–thaw cycles on meat quality,nutrients, water distribution and microstructure in bovine rumen smooth muscle

This study investigated the effect of 5 freeze–thaw cycles (freezing at −18°C for 12 h and then thawing at 4°C for approximately 12 h) on the meat quality, proximate composition, water distribution and microstructure of bovine rumen smooth muscle (BSM). As the number of freeze–thaw cycles increased, BSM pH, shear force, water content and protein content decreased by 3.06%, 35.50%, 14.49% and 21.11%, respectively, whereas BSM thawing loss, cooking loss, pressing loss, total aerobic count (TAC), ash content and fat content increased by 108.12%, 47.75%, 78.33%, 90.99%, 105% and 35.20%, respectively. The freeze–thaw cycles resulted in greater protein and lipid oxidation, as evidenced by a 36.46% reduction in the sulfhydryl content and a 209.06% and 338.46% increase in the carbonyl and malondialdehyde contents, respectively. Ice crystal formation disrupted the structural integrity of the muscle tissue. Low-field nuclear magnetic resonance results showed that the freeze–thaw cycles prolonged the relaxation times (T_2b, T₂₁ and T₂₂), indicating that immobile water shifted to free water, and consequently, free water mobility increased. After 3 freeze–thaw cycles, the decline in shear force slowed, the increase in thawing loss became accelerated, and the TAC approached the domain value (6 log colony-forming units/g). Therefore, the number of freeze–thaw cycles of smooth muscle during transport, storage and distribution should be controlled to 3 or fewer. The current results provide a theoretical basis and data support for the further utilisation and culinary processing of smooth muscle.     

Influence of thermal runaway in styrene–acrylonitrile bulk copolymerization revealed by computational fluid dynamics modeling

The computational fluid dynamics (CFD) and kinetic-based moment methods coupled approach is adopted to simulate the bulk copolymerization of styrene–acrylonitrile (SAN) in a stirred tank reactor. Numerical simulations are carried out to investigate the impacts of impeller speed, monomer ratio, initiator ratio, and initial reaction temperature on the copolymerization process and product properties. Particularly, the Chaos theory is selected as a criterion for evaluating the occurrence of the thermal runaway. The Flory's and Stockmayer's distributions are employed to calculate chain length distribution and copolymer composition distribution of copolymer. The simulation results highlight that the appearance of thermal runaway can be postponed by properly increasing the rotation speed, decreasing the initiator loadings, initial acrylonitrile contents and initial reactor temperature. Furthermore, significant differences exist in the product properties that predicted by the ideal and non-ideal models, which demonstrates that the temperature heterogeneity plays a crucial role in SAN copolymerization. This study could offer references for the safe operation and design of polymerization processes.     

Improved thermal stability of the near-infrared Al-modulated Zn3Ga2GeO8: Cr3+ phosphors for plant growth applications

The exploration of the high thermal stability near-infrared (NIR) phosphors is significantly crucial for the development of plant lighting. However, NIR phosphors suffer from the poor chemical and thermal stability, which severely limits their long-term operation. Here, the successful improvement of luminous intensity (149.5%) and thermal stability at 423 K of Zn₃Ga₂GeO₈ (ZGGO): Cr³⁺ phosphors is achieved for the introduction of Al³⁺ ions into the host. The release of carriers in deep traps inhibits the emission loss for the thermal disturbance. Furthermore, an NIR light emitting diodes (LEDs) lamp is explored by combining the optimized Zn₃Ga_1.1675Al_0.8GeO₈: 0.0325Cr³⁺ phosphors with a commercial 460 nm blue chip, and the emission band can match well with the absorption bands of photosynthetic pigments and the phytochrome (P_R and P_FR) of plants. The explored LEDs lamp further determines the growth and the pheromone content of the involved plants for the participation of the NIR emission originated from Cr³⁺ ions. Our work provides a promising NIR lamp as plant light with improved thermal stability for long-term operation.     

Preparation of high-purity SiC ceramics with good plasma corrosion resistance by hot-pressing sintering

High-purity SiC ceramic devices are applied in semiconductor industry owing to their outstanding properties. Nevertheless, it is difficult to densify SiC ceramics without any sintering additive even by HP sintering. In this work, high-purity and dense SiC ceramics were fabricated by HP sintering with very low amounts of sintering aids. Residual B content was only 556 ppm and relative density was more than 99.5%. Furthermore, thermal conductivity of as-prepared SiC ceramics was improved from 155 W m^?1 K^?1 to 167 W m^?1 K^?1 by increasing holding time and their plasma corrosion resistance was promoted in the meantime. The as-prepared high-purity SiC ceramics have broad application prospects in the field of semiconductor industry.     

Behavior of phase transformation of Baotou mixed rare earth concentrate during oxidation roasting

Based on the new process named “Combination Method” for metallurgy and separation of Baotou mixed rare earth concentrate (BMREC), the aim of this paper is to clearly elucidate the phase change behavior of BMREC without additives during oxidative roasting at 450–800 °C. The results indicate that the bastnaesite in BMREC is decomposed at 450–550 °C, the weight loss is about 10.3 wt%, and the activation energy (E) is 144 kJ/mol. The bastnaesite in BMREC is decomposed into rare earth fluoride, rare earth oxides (La₂O₃, Ce₇O₁₂, Pr₆O₁₁ and Nd₂O₃), and CO₂, particularly, with the increase of roasting temperature, bastnaesite in BMREC is more completely decomposed into LaF₃, which causes a decrease in leaching rate of La during the HCl leaching process. Additionally, the maximum cerium oxidation efficiency reaches about 60 wt% when the roasting temperature is equal to or above 500 °C, and the oxidation reaction rate of cerium increases with the increasing roasting temperature.     

Unraveling specific role of carbon matrix over Pd/quasi-Ce-MOF facilitating toluene enhanced degradation

Metal organic frameworks (MOFs) derivatives represented by quasi-MOFs have excellent physical and chemical properties and can be applied for the catalytic combustion of volatile organic compounds (VOCs). In this work, Pd/quasi-Ce-BTC synthesized by simple one-step N₂ pyrolysis was applied to the oxidation of toluene, showing excellent toluene catalytic activity (T₉₀ = 175 °C, 30000 mL/(g·h)). Microscopic analyses indicate the formation and interaction of a carbon matrix composite quasi-MOF structure interface. The results show that the amorphous carbon matrix formed during the partial pyrolysis of Ce-BTC significantly improves the adsorption and activation capacity of toluene in the reaction, and constructs a reductive system to maintain high concentrations of Ce³⁺ and Pd⁰, which can facilitate the activation and utilization of oxygen in reaction. Quasi in-situ XPS proves that carbon matrix is indirectly involved in the activation and storage of oxygen, and Pd⁰ is the crucial active site for the activation of oxygen. Stability and water resistance tests display good stability of Pd/quasi-Ce-BTC. This work provides a potential method for designing quasi-MOF catalysts towards VOCs effective abatement.