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。     

建筑物掏土纠倾法单孔与多孔塑性区特性研究及工程应用

在建筑物水平掏土纠倾工程中，掏土孔间距是影响纠倾工程安全与工期的重要因素。为了快速准确地确定纠倾工程中的水平掏土孔间距，研究了单个掏土孔和多个掏土孔情况下孔周边土体塑性区发展特性。利用土体塑性力学分析计算得到了单孔下的孔周土塑性区半径，而后通过有限元模拟得到孔周土体塑性区半径的数值解，将孔周塑性区半径解析解与数值解进行了对比。并通过有限元数值模型研究了多个掏土孔相互影响情况下的塑性区发展规律，以孔间土体塑性区贯通时的距离作为掏土孔间距。考虑土体参数随机特性的影响，研究不同上部荷载作用下掏土孔间距的取值变化规律，上部面荷载与地基承载力特征值比值用p表示，孔间距与掏土孔直径比值用n表示。研究发现：多孔塑性区半径（孔间塑性区贯通时）是单孔塑性区半径的1.3倍左右;标准化荷载p与孔间距比值n二者呈线性关系;通过不同土体参数及上部荷载的不同情况下的p-n曲线，给出了掏土孔间距建议值。同时，将研究结果与三个实际工程进行对比，发现p-n曲线法与实际结果更为接近。     

Fabrication and comprehensive structural and spectroscopic properties of Er:Y2O3 transparent ceramics

Transparent Er:Y₂O₃ ceramics with sub-micron grain size (<1 μm) were fabricated by using one-step vacuum sintering followed by hot isostatic pressing (HIPing) technique. The transmission of the undoped Y₂O₃ reaches 83%. The structural characteristics including the phonon energy were investigated through X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) analysis and scanning electron microscopy (SEM) measurement. The overall spectroscopic properties of transmission, fluorescence emission up to 3000 nm, lifetime, up-conversion luminescence, and refractive index were systematically studied for both 0.25 at% and 7.0 at% Er:Y₂O₃ ceramics with different thicknesses. The comparison of the spectra of the fluorescence emission and up-conversion luminescence under both 976 and 808 nm laser excitation was performed. The multiple high-energy-state transitional processes after the excited state absorption (ESA) processes involved in the up-conversion are discriminated between the multi-phonon non-radiative transitions and the radiative transitions according to the measured maximum phonon vibrational energy. The calculation was performed based on the Judd–Ofelt theory.     

Fluorescence Correlation Spectroscopy Analysis of Effect of Molecular Crowding on Self-Assembly of β-Annulus Peptide into Artificial Viral Capsid

Recent progress in the de novo design of self-assembling peptides has enabled the construction of peptide-based viral capsids. Previously, we demonstrated that 24-mer β-annulus peptides from tomato bushy stunt virus spontaneously self-assemble into an artificial viral capsid. Here we propose to use the artificial viral capsid through the self-assembly of β-annulus peptide as a simple model to analyze the effect of molecular crowding environment on the formation process of viral capsid. Artificial viral capsids formed by co-assembly of fluorescent-labelled and unmodified β-annulus peptides in dilute aqueous solutions and under molecular crowding conditions were analyzed using fluorescence correlation spectroscopy (FCS). The apparent particle size and the dissociation constant (K_d) of the assemblies decreased with increasing concentration of the molecular crowding agent, i.e., polyethylene glycol (PEG). This is the first successful in situ analysis of self-assembling process of artificial viral capsid under molecular crowding conditions.