Swapping catalytic active sites from cationic Ni to anionic F in Fe–F–Ni3S2 enables more efficient alkaline oxygen evolution reaction and urea oxidation reaction

Electrolysis of water for producing hydrogen instead of traditional fossil fuels is one of the most promising methods to alleviate environmental pollution and energy crisis. In this work, Fe and F ion co-doped Ni₃S₂ nanoarrays grown on Ni foam substrate were prepared by typical hydrothermal and sulfuration processes for the first time. Density functional theory (DFT) calculation demonstrate that the adsorption energy of the material to water is greatly enhanced due to the doping of F and Fe, which is conducive to the formation of intermediate species and the improvement of electrochemical performance of the electrode. The adsorption energy of anions (F and S) and cations (Fe and Ni) to water in each material was also calculated, and the results showed that F ion showed the most optimal adsorption energy of water, which proved that the doping of F and Fe was beneficial to improve the electrochemical performance of the electrode. It is worth noting that the surface of Fe–F–Ni₃S₂ material will undergo reconstruction during the process of water oxidation reaction and urea oxidation reaction, and amorphous oxides or hydroxides in situ would be formed on the surface of electrode, which are the real active species.     

Generalized differential quadrature analysis of MHD mixed convective motion of Casson fluids past an isothermal irregular slender geometry via Cattaneo–Christov's approach

Classical Fourier's theory is well-known in continuum physics and thermal sciences. However, the primary drawback of this law is that it contradicts the principle of causality. To explore the thermal relaxation time characteristic, Cattaneo–Christov's theory is adopted thermally. In this regard, the features of magnetohydrodynamic (MHD) mixed convective flows of Casson fluids over an impermeable irregular sheet are revealed numerically. In addition, the resulting system of partial differential equations is altered via practical transformations into nonlinear ordinary differential equations. An advanced numerical algorithm is developed in this respect to get higher approximations for temperature and velocity fields, as well as their corresponding wall gradients. For validating our numerical code, the current outcomes are compared with the available literature results. Moreover, it is revealed that the velocity field is more prominent in the suction flow situation as compared with the injection flow case. It is also found that the Casson fluid is hastened in the case of lower yield stress. Larger values of thermal relaxation parameters create a lessening trend in the temperature distribution and its related boundary layer breadth.     

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。     

Role of functionalized graphene quantum dots in hydrogen evolution reaction: A density functional theory study

Rapid advances in the field of catalysis require a microscopic understanding of the catalytic mechanisms. However, in recent times, experimental insights in this field have fallen short of expectations. Furthermore, experimental searches of novel catalytic materials are expensive and time-consuming, with no guarantees of success. As a result, density functional theory (DFT) can be quite advantageous in advancing this field because of the microscopic insights it provides and thus can guide experimental searches of novel catalysts. Several recent works have demonstrated that low-dimensional materials can be very efficient catalysts. Graphene quantum dots (GQDs) have gained much attention in past years due to their unique properties like low toxicity, chemical inertness, biocompatibility, crystallinity, etc. These properties of GQDs which are due to quantum confinement and edge effects facilitate their applications in various fields like sensing, photoelectronics, catalysis, and many more. Furthermore, the properties of GQDs can be enhanced by doping and functionalization. In order to understand the effects of functionalization by oxygen and boron based groups on the catalytic properties relevant to the hydrogen-evolution reaction (HER), we perform a systematic study of GQDs functionalized with the oxygen (O), borinic acid (BC₂O), and boronic acid (BCO₂). All calculations that included geometry optimization, electronic and adsorption mechanism, were carried out using the Gaussian16 package, employing the hybrid functional B3LYP, and the basis set 6-31G(d,p). With the variation in functionalization groups in GQDs, we observe significant changes in their electronic properties. The adsorption energy E_ads of hydrogen over O-GQD, BC₂O-GQD, and BCO₂-GQD is ?0.059 eV, ?0.031 eV and ?0.032 eV respectively. Accordingly, Gibbs free energy (ΔG) of hydrogen adsorption is extraordinarily near the ideal value (0 eV) for all the three types of functionalized GQDs. Thus, the present work suggests pathways for experimental realization of low-cost and multifunctional GQDs based catalysts for clean and renewable hydrogen energy production.     

Crystallization behavior and density functional theory study of solution combustion synthesized silicon doped calcium phosphates

The influence of heat-treatment temperatures (700 °C, 900°C, 1200 °C) on the phase, physical properties, crystallization rate, and in vitro properties of the solution combustion synthesized silicon-doped calcium phosphates (CaPs) were investigated. The thermodynamic aspects (enthalpy, entropy, and free energy) of the synthesis process and the crystallographic properties of the final samples were first predicted and then confirmed using density functional theory (DFT). Results demonstrated that the crystallization rate was controlled by the fuel(s) type (glycine, citric acid, and urea) and the amounts of Si⁴⁺ ions (0, 0.1, 0.4 mol). The highest calculated crystallization rate values of the un-doped, 0.1, and 0.4 mol Si-doped samples were 64%, 22%, 38%, respectively. The obtained results from the DFT simulation revealed that crystal growth in the direction of c-axis of hydroxyapatite (HAp) structure could change the stability of (001) surface of (HAp). Also, the computational data confirmed the adsorption of Si–OH groups on the (001) surface of HAp during the SCS process with an adsorption energy of 1.53 eV. AFM results in line with DFT simulation showed that the observed change in the surface roughness of Si-doped CaPs from 2 to 8 nm could be related to the doping of Si⁴⁺ ions onto the surface of CaPs. Besides, the theoretical and experimental investigation showed that crystal growth and doping of Si⁴⁺ ions could decrease the activation energy of oxygen reduction reaction (ORR). Furthermore, the results showed that the crystallized HAp structure could have great potential to efficiently reduce oxidative stress in human body.     

饱和块状混合回填土地基的一维固结分析

用块状渣土置换软弱地基和回填低洼谷地等是处置工程渣土的有效途径。为了分析饱和块状混合回填土地基的固结性状，运用混合物理论建立了其一维固结模型。首先，假定块状土固相和充填土固相之间满足等应变条件，获得了饱和块状混合回填土中各相应变与块状土孔隙变形和充填土孔隙变形的关系式。其次，在小应变条件下，根据自由能势函数方程建立了饱和块状混合回填土的一维线弹性本构方程，再结合达西定律和应力平衡方程获得了一维固结控制方程。再次，利用分离变量法得到一维固结解析解，通过退化本文模型与已有模型进行对比，验证了本文模型的正确性。最后，基于所得解析解，分析了充填土孔隙渗透系数、块状土孔隙渗透系数以及流体交换参数等因素对饱和块状混合回填土地基固结性状的影响。分析结果表明：充填土孔隙渗透系数对饱和块状混合回填土地基整体固结性状起主导作用；在固结初期，块状土超孔压会有一定程度的上升，且3个参数具有相似的作用机理。     

Post-erosion mechanical responses of internally unstable gap-graded soil under drained torsional simple shear and triaxial compression

Internal erosion is a major threat to hydraulic earth structures, such as river levees and dams. This paper focuses on suffusion and suffosion phenomena which are caused by the movement of fine particles in the granular skeleton due to seepage flow. The present study investigates the impact of internal erosion on the dynamic response under cyclic torsional shear and monotonic responses under triaxial compression and torsional simple shear. A series of experiments, using a gap-graded silica mixture with a fines content of 20%, is performed under loose, medium, and dense conditions using a novel erosion hollow cylindrical torsional shear apparatus. The erosion test results indicate that the critical hydraulic gradient and the rate of erosion are density-dependent, where a transition from suffosion to suffusion is observed as the seepage continues. Regardless of the sample density, variations in the radial strain and particle size distribution, along the specimen height after erosion, are no longer uniform. Furthermore, the dynamic shearing results show that the small-strain shear modulus increases, but the initial damping ratio decreases after internal erosion, probably due to the removal of free fines. In addition, the elastic threshold strain and reference shear strain values are found to be higher for the eroded and non-eroded specimens, respectively. Finally, based on drained monotonic loading, the post-erosion peak stress ratio increases remarkably under triaxial compression, while that under torsional simple shear depends on the relative density where the direction of loading is normal to the direction of seepage. These observations indicate that the horizontal bedding plane becomes weaker, while the vertical one becomes stronger after downward erosion.     

Liquefaction behavior of fiber-reinforced calcareous sands in unidirectional and multidirectional simple shear tests

A study on the liquefaction resistance of calcareous sands reinforced with polypropylene fibers was reported. Stress-controlled cyclic simple shear tests were conducted on specimens prepared at a relative density of 50%, with and without fiber reinforcements. The liquefaction behavior was investigated by considering the effects of fiber contents ranging from 0% to 1%, fiber lengths varying from 3 mm to 12 mm and loading patterns. The results indicated that increasing fiber content and fiber length resulted in a decrease in the deformation, a reduction in pore pressure accumulation rate, and improved the liquefaction resistance of calcareous sands. Additionally, the risk of soil liquefaction could be significantly reduced when the fiber content was greater than 0.8%. The multidirectional loading had a considerable effect in reducing the liquefaction resistance compared to unidirectional loading. Further, the stiffness degradation of calcareous sands decreased with increasing fiber content and fiber length. The pore pressure generated in the cyclic tests was analyzed and was found to be affected by fiber content. A pore pressure prediction model was proposed to obtain the pore pressure characteristics of fiber-reinforced calcareous sands under various fiber content conditions.     

Evaluation of back-calculated elastic moduli of unreinforced and geocell-reinforced unbound granular material from full-scale field tests

This paper presents a field-scale experimental track over a poor subgrade with an unreinforced section and a geocell-reinforced section subjected to in-situ performance tests. Plate load tests and Benkelman beam tests were carried out distributed in several unreinforced and reinforced layers. The objective was to: (1) examine the variability of the elastic modulus of unbound granular material (UGM) due the influence of its thickness and the presence of poor subgrade in its base, (2) evaluate the modulus improvement factor (MIF) generated by the geocell reinforcement in the UGM and (3) verify the most appropriate condition to apply the MIF to transport infrastructure design. The results showed that there is a significant influence of the thickness of the UGM layer on its elastic modulus when the layer is supported directly over a soft subgrade. The MIF values obtained in field suggest that its determination is mostly related to the UGM maximum elastic modulus rather than its decreased values (by virtue of poor subgrade or reduced thicknesses), and that the analytical formulation presented for MIF calculation has good predictive capability to be applied to pavement design.