Fe(III) grafted MoO3 nanorods for effective electrocatalytic fixation of atmospheric N2 to NH3

Electrocatalytic nitrogen reduction reaction (ENRR) offers a carbon-neutral process to fix nitrogen into ammonia, but its feasibility depends on the development of highly efficient electrocatalysts. Herein, we report that Fe ion grafted on MoO₃ nanorods synthesized by an impregnation technique can efficiently enhance the electron harvesting ability and the selectivity of H⁺ during the NRR process in neutral electrolyte. In 0.1 M Na₂SO₄ solution, the electrocatalyst exhibited a remarkable NRR activity with an NH₃ yield of 9.66 μg h^?1 mg^?1_cat and a Faradaic efficiency (FE) of 13.1%, far outperforming the ungrafted MnO₃. Density functional theory calculations revealed that the Fe sites are major activation centers along the alternating pathway.     

基于分形理论的黄河内蒙古段河势演变特征及其与凌汛灾害关联研究

寒区河道凌汛灾害河势“弯道效应”的量化评估十分重要。基于分形理论提出河道横断面-纵剖面-平面多维度河势分形维数计算方法及其物理机制，并探讨黄河内蒙古段不同维度河势演变分形特征及其与凌汛灾害的关联关系。结果表明，黄河内蒙古段不同维度河势均具有多尺度自相似分形特征，且具有多年记忆周期的长程相关性；冰坝（严重性冰塞）发生频次与河道主槽弯曲分形维数呈正相关指数型函数关系，与河相系数、深泓点高程和河段平均底坡分形维数负相关，与水深-面积分形维数正相关，总体表明冰坝灾害更易发生于主槽偏移摆动大、蜿蜒曲折、河湾发育程度高的宽浅型弯曲河道，研究成果可为凌汛期冰塞冰坝灾害易发河段诊断及预测提供重要理论依据。     

Density functional theory study of the hydrogen evolution reaction in haeckelite boron nitride quantum dots

To satisfy arising energy needs and to handle the forthcoming worldwide climate transformation, the major research attention has been drawn to environmentally friendly, renewable and abundant energy resources. Hydrogen plays an ideal and significant role is such resources, due to its non-carbon based energy and production through clean energy. In this work, we have explored catalytic activity of a newly predicted haeckelite boron nitride quantum dot (haeck-BNQD), constructed from the infinite BN sheet, for its utilization in hydrogen production. Density functional theory calculations are employed to investigate geometry optimization, electronic and adsorption mechanism of haeck-BNQD using Gaussian16 package, employing the hybrid B3LYP and wB97XD functionals, along with 6–31G(d,p) basis set. A number of physical quantities such as HOMO/LUMO energies, density of states, hydrogen atom adsorption energies, Mulliken populations, Gibbs free energy, work functions, overpotentials, etc., have been computed and analysed in the context of the catalytic performance of haeck-BNQD for the hydrogen-evolution reaction (HER). Based on our calculations, we predict that the best catalytic performance will be obtained for H adsorption on top of the squares or the octagons of haeck-BNQD. We hope that our prediction of most active catalytic sites on haeck-BNQD for HER will be put to test in future experiments.     

疫情下电磁场理论课程的网络教学

本文主要总结了新冠疫情期间作者的电磁场理论课程在线教学经验。对比分析了录播和直播的优缺点后,选择录播教学方式。基于超星网络教学平台,展示了录播网络教学的具体措施,包括网上答疑和学习效果检查以及在线批改作业等。给出了网络教学可以为线下教学继续使用的方法和手段,为疫情结束后的正常教学提供了新的网络教学补充措施。     

Engineering the hydrogen storage properties of the perovskite hydride ZrNiH3 by uniaxial/biaxial strain

In the present work, the bonding length, electronic structure, stability, and dehydrogenation properties of the Perovskite-type ZrNiH₃ hydride, under different uniaxial/biaxial strains are investigated through ab-initio calculations based on the plane-wave pseudo-potential (PW-PP) approach. The findings reveal that the uniaxial/biaxial compressive and tensile strains are responsible for the structural deformation of the ZrNiH₃ crystal structure, and its lattice deformation becomes more significant with decreasing or increasing the strain magnitude. Due to the strain energy contribution, the uniaxial/biaxial strain not only lowers the stability of ZrNiH₃ but also decreases considerably the dehydrogenation enthalpy and decomposition temperature. Precisely, the formation enthalpy and decomposition temperature are reduced from ?67.73 kJ/mol.H₂ and 521 K for non-strained ZrNiH₃ up to ?33.73 kJ/mol.H₂ and 259.5 K under maximal biaxial compression strain of ε = ?6%, and to ?50.99 kJ/mol.H₂ and 392.23 K for the maximal biaxial tensile strain of ε = +6%. The same phenomenon has been also observed for the uniaxial strain, where the formation enthalpy and decomposition temperature are both decreased to ?39.36 kJ/mol.H₂ and 302.78 K for a maximal uniaxial compressive strain of ε = - 12%, and to ?51.86 kJ/mol.H₂ and 399 K under the maximal uniaxial tensile strain of ε = +12%. Moreover, the densities of states analysis suggests that the strain-induced variation in the dehydrogenation and structural properties of ZrNiH₃ are strongly related to the Fermi level value of total densities of states. These ab-initio calculations demonstrate insightful novel approach into the development of Zr-based intermetallic hydrides for hydrogen storage practical applications.     

Carbon corrosion mechanism on nitrogen-doped carbon support — A density functional theory study

In this work, density functional theory (DFT) calculations were used to investigate the mechanism of carbon corrosion on nitrogen-doped carbon support. Free energy diagrams were generated based on three proposed reaction pathways to evaluate corrosion mechanisms. The most energetically preferred mechanism on nitrogen-doped carbon was determined. The results show that the step of water dissociation to form ^#OH was the rate-determining step for gra-G-1N (graphene doped with graphitic N) and pyrr-G-1N (graphene doped with pyrrolic N). As for graphene doped with pyridinic N, the step of C^#OC^#O formation was critical. It was found that the control of nitrogen concentration was necessary for precisely designing optimized carbon materials. Abundance of nitrogen moieties aggravated the carbon corrosion. When the high potential was applied, specific types of graphitic N and pyridinic N were found to be favorable carbon modifications to improve carbon corrosion resistance. Moreover, the solvent effect was also investigated. The results provide theoretical insights and design guidelines to improve corrosion resistance in carbon support through material modification by inhibiting the adsorption of surface oxides (OH, O, and OOH).     

Lithiation MXene Derivative Skeletons for Wide-Temperature Lithium Metal Anodes

Lithium (Li) metal, as an appealing candidate for the next-generation of high-energy-density batteries, is plagued by its safety issue mainly caused by uncontrolled dendrite growth and infinite volume expansion. Developing new materials that can improve the performance of Li-metal anode is one of the urgent tasks. Herein, a new MXene derivative containing pure rutile TiO₂ and N-doped carbon prepared by heat-treating MXene under a mixing gas, exhibiting high chemical activity in molten Li, is reported. The lithiation MXene derivative with a hybrid of LiTiO₂-Li₃N-C and Li offers outstanding electrochemical properties. The symmetrical cell assembling lithiation MXene derivative hybrid anode exhibits an ultra-long cycle lifespan of 2000 h with an overpotential of ≈30 mV at 1 mA cm⁻², which overwhelms Li-based anodes reported so far. Additionally, long-term operations of 34, 350, and 500 h at 10 mA cm⁻² can be achieved in symmetrical cells at temperatures of −10, 25, and 50 °C, respectively. Both experimental tests and density functional theory calculations confirm that the LiTiO₂-Li₃N-C skeleton serves as a promising host for Li infusion by alleviating volume variation. Simultaneously, the superlithiophilic interphase of Li₃N guides Li deposition along the LiTiO₂-Li₃N-C skeleton to avoid dendrite growth.     

Thermal desorption and pyrolysis direct analysis in real time mass spectrometry of Nafion membrane

Perfluorosulfonic acid ionomer membranes have been widely used as proton conducting membranes in various electrochemical processes such as polymer electrolyte fuel cells and water electrolysis. While their thermal stability has been studied by thermogravimetry and analysis of low molecular weight products, their decomposition mechanism is little understood. In this study a newly developed methodology of thermal desorption and pyrolysis in combination with direct analysis in real time mass spectrometry is applied for Nafion membrane. An ambient ionization source and a high-resolution time-of-flight mass spectrometer enabled unambiguous assignment of gaseous products. Thermal decomposition is initiated by side chain detachment above 350°C, which leaves carbonyls on the main chain at the locations of the side chains. Perfluoroalkanes are released above 400°C by main chain scission and their further decomposition products dominate above 500 °C. DFT calculation of reaction energies and barrier heights of model compounds support proposed decomposition reactions.     

Breeding schemes with optimum-contribution selection or truncation selection for beef cattle destined for use on dairy females

We tested the hypothesis that the size of a beef cattle population destined for use on dairy females is smaller under optimum-contribution selection (OCS) than under truncation selection (TRS) at the same genetic gain (ΔG) and the same rate of inbreeding (ΔF). We used stochastic simulation to estimate true ΔG realized at a 0.005 ΔF in breeding schemes with OCS or TRS. The schemes for the beef cattle population also differed in the number of purebred offspring per dam and the total number of purebred offspring per generation. Dams of the next generation were exclusively selected among the one-year-old heifers. All dams were donors for embryo transfer and produced a maximum of 5 or 10 offspring. The total number of purebred offspring per generation was: 400, 800, 1,600 or 4,000 calves, and it was used as a measure of population size. Rate of inbreeding was predicted and controlled using pedigree relationships. Each OCS (TRS) scheme was simulated for 10 discrete generations and replicated 100 (200) times. The OCS scheme and the TRS scheme with a maximum of 10 offspring per dam required approximately 783 and 1,257 purebred offspring per generation to realize a true ΔG of €14 and a ΔF of 0.005 per generation. Schemes with a maximum of 5 offspring per dam required more purebred offspring per generation to realize a similar true ΔG and a similar ΔF. Our results show that OCS and multiple ovulation and embryo transfer act on selection intensity through different mechanisms to achieve fewer selection candidates and fewer selected sires and dams than under TRS at the same ΔG and a fixed ΔF. Therefore, we advocate the use of a breeding scheme with OCS and multiple ovulation and embryo transfer for beef cattle destined for use on dairy females because it is favorable both from an economic perspective and a carbon footprint perspective.     

Prediction of mode I fracture toughness of rock using linear multiple regression and gene expression programming

Prediction of mode I fracture toughness (K_IC) of rock is of significant importance in rock engineering analyses. In this study, linear multiple regression (LMR) and gene expression programming (GEP) methods were used to provide a reliable relationship to determine mode I fracture toughness of rock. The presented model was developed based on 60 datasets taken from the previous literature. To predict fracture parameters, three mechanical parameters of rock mass including uniaxial compressive strength (UCS), Brazilian tensile strength (BTS), and elastic modulus (E) have been selected as the input parameters. A cluster of data was collected and divided into two random groups of training and testing datasets. Then, different statistical linear and artificial intelligence based nonlinear analyses were conducted on the training data to provide a reliable prediction model of K_IC. These two predictive methods were then evaluated based on the testing data. To evaluate the efficiency of the proposed models for predicting the mode I fracture toughness of rock, various statistical indices including coefficient of determination (R²), root mean square error (RMSE), and mean absolute error (MAE) were utilized herein. In the case of testing datasets, the values of R², RMSE, and MAE for the GEP model were 0.87, 0.188, and 0.156, respectively, while they were 0.74, 0.473, and 0.223, respectively, for the LMR model. The results indicated that the selected GEP model delivered superior performance with a higher R² value and lower errors.