A high temperature and pressure framework for supercritical water electrolysis

Water electrolysis technologies aim to provide a significant increase in green hydrogen production efficiency. In this work, a framework was developed to explore the use of supercritical water for alkaline electrolysis. This framework was used to perform Arrhenius analysis as a function of potential, and to explore activation energies for sub- and supercritical water electrolysis. An analysis of the conductivity of solution unveiled a discontinuity in the trends between sub- and supercritical potassium hydroxide solution conductivity. Unlike prior work on supercritical water electrolysis, this work investigates trends in electrochemical parameters, the sources of these trends, and how they change between the sub- and supercritical regimes.     

Revealing the role of Ni2+ ions in inducing the synthesis of porous carbon balls: A novel substrate to enhance the Pt catalytic activity towards methanol-oxidation

Carbon-based materials have been often employed as electrocatalytic substrates because of their large surface area/highly porous structure. Similar to carbon substrates, the non-carbon related materials such as transition metals also play an important role in improving catalytic performance. However, the simultaneous synthesis and metallic functionalization of carbon substrates is a highly challenging issue. Herein, a hydrothermal method has been used for the preparation of Ni-functionalized porous carbon balls. The significant role of Ni²⁺ ions in the synthesis of porous carbon balls has been confirmed. The results of transmission electron microscopy indicate that, the as-prepared porous carbon balls were suitable for the dispersion of Pt nanoparticles with small particle size (less than 4 nm). In addition to providing the OH_ads species, the Ni can also modify the surface electronic structure of Pt. Electrochemical measurements results reveal that, under the strong interactions between Ni and Pt, the as-prepared porous carbon balls supported Pt nanoparticles (Pt/Ni-CB) catalyst possesses excellent electrocatalytic activity, stability and CO anti-poisoning capability towards methanol electrooxidation reaction (MOR). This work opens a novel idea for the construction of the metal functionalization of carbon substrates and their subsequent applications in other electrocatalytic reactions.     

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.     

Effect of support and reduction temperature in the hydrogenation of CO2 over the Cu–Pd bimetallic catalyst with high Cu/Pd ratio

Metal-support interaction and catalyst pretreatment are important for industrial catalysis. This work investigated the effect of supports (SiO₂, CeO₂, TiO₂ and ZrO₂) for Cu–Pd catalyst with high Cu/Pd ratio (Cu/Pd = 33.5) regarding catalyst cost, and the reduction temperatures of 350 °C and 550 °C were compared. The activity based on catalyst weight follows the order of Si > Ce > Zr > Ti when reduced at 350 °C. The reduction temperature leads to the surface reconstruction over the SiO₂, CeO₂ and TiO₂ catalysts, while results in phase transition over Cu–Pd/ZrO₂. The effect of reduction temperature on catalytic performance is prominent for the SiO₂ and ZrO₂ supported catalysts but not for the CeO₂ and TiO₂ ones. Among the investigated catalysts, Zr-350 exhibits the highest methanol yield. This work reveals the importance of the supports and pretreatment conditions on the physical-chemical properties and the catalytic performance of the Cu–Pd bimetallic catalysts.     

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.     

超高分子量聚乙烯纤维增强中空蜂窝模压复合材料性能研究

为研制车船等壳体所用的轻质、高强复合板材,选用超高分子量聚乙烯(UHMWPE)短纤维纱,制备成单层经纬为120根/(10 cm)的平纹组织,采用多组经纱持续更替交织层的方法制成2L(1+0)型、4L(2+1)型、6L(3+2)型3种多层角联锁结构织物,采用扦插芯棒、模压成型方法制成菱形蜂窝状的热固性环氧树脂基中空板,并与2块真空吸液法制成的面板组成“三合一”复合板,同时测定了复合板材的结构特征及其平拉、平压和弯曲性能。结果表明:3种类型复合板的密度均远小于水的密度,其中6L(3+2)型最小,为0.48 g/cm³;复合板层数越多,环氧树脂越难渗透尤其是在中空板菱形交叉点处,复合板平拉、平压、抗弯曲强度则呈现递增,制成的6L(3+2)型复合板试样平压强度可达到1.03 MPa。     

A new method for extrapolating the load-displacement response of drilled shaft foundations for interpretation of side capacity

In this study, the side capacity of drilled shaft foundations is estimated from partially-mobilized load–displacement field data using a new method in the extrapolation of load–displacement response. A dataset of 138 bi-directional load tests is used to evaluate the degree of mobilization of unit side resistance. A total of 612 unit side-resistance curves obtained from measured strain gauge recordings are utilized in this study. The proposed extrapolation approach is based on a new technique, the Double Tangent method, characterizing the extent of mobilization for each unit side-resistance curve. Roughly, 12% of the dataset exhibits a fully-mobilized load–displacement response, with the remainder exhibiting varying degrees of a partially-mobilized response. Fully-mobilized records are further characterized using the Double Tangent method over different ranges of mobilization, resulting in four regression models based on predominant soil types. Each model is assessed statistically, and a global regression model is found suitable to predict maximum unit side resistance. The global model is further validated using two independent load test datasets, comparing measured values of unit side resistance against predicted values. The model is then used to predict maximum unit side resistance for all partially-mobilized data within the dataset, and the results are compared to two extrapolation techniques currently used in practice. The corresponding resistance-displacement response is extrapolated using a proposed asymptotic curve-fitting function for side resistance, and an example extrapolation is illustrated to showcase how the proposed method can be used in engineering practice.