Optimizing the Oxygen-Catalytic Performance of Zn–Mn–Co Spinel by Regulating the Bond Competition at Octahedral Sites

By using the more electro-negative Mn³⁺ ion to partially replace Co³⁺ at the octahedral site of spinel ZnCo₂O₄, i.e., forming ternary Zn–Mn–Co spinel oxide, the electrocatalytic oxygen reduction/evolution activity is found to be significantly increased. Considering the physical characterization and theoretical calculations, it demonstrated that the bond competition played a key role in regulating the cobalt valence state and the electrocatalytic activity. The partial replacement of octahedral-site-occupied Co³⁺ by Mn³⁺ can effectively modulate the adjacent Co–O bond and induce the Jahn–Teller effect, thus changing the originally stable crystal structure and optimizing the binding strength between the active center and reaction intermediates. Certainly, the Mn-substituted ZnMn_1.4Co_0.6O₄/NCNTs exhibit higher electrocatalytic oxygen reduction reaction (ORR) activity than that of ZnCo₂O₄/NCNTs and ZnMn₂O₄/NCNTs, supporting that the Co–O bond covalency determines the ORR activity of spinel ZnCo₂O₄. This study offers the competition between adjacent Co–O and Mn–O bonds via the B_Oh–O–B_Oh edge-sharing geometry. The ion substitution at octahedral sites by less electronegative cations can be a new and effective way to improve the electrocatalytic performance of cobalt-based spinel oxides.     

Surface Oxygen Coordination of Hydrogen Bond Chemistry for Aqueous Ammonium Ion Hybrid Supercapacitor

Aqueous ammonium ion hybrid supercapacitor (A-HSC) combines the charge storage mechanisms of surface adsorption and bulk intercalation, making it a low-cost, safe, and sustainable energy storage candidate. However, its development is hindered by the low capacity and unclear charge storage fundamentals. Here, the strategy of phosphate ion-assisted surface functionalization is used to increase the ammonium ion storage capacity of an α-MoO₃ electrode. Moreover, the understanding of charge storage mechanisms via structural characterization, electrochemical analysis, and theoretical calculation is advanced. It is shown that NH₄⁺ intercalation into layered α-MoO₃ is not dominant in the A-HSC system; rather, the charge storage mainly depends on the adsorption energy of surface “O” to NH₄⁺. It is further revealed that the hydrogen bond chemistry of the coordination between “O” of surface phosphate ion and NH₄⁺ is the reason for the capacity increase of MoO₃. This study not only advances the basic understanding of rechargeable aqueous A-HSC but also demonstrates the promising future of surface engineering strategies for energy storage devices.     

A mechanistic approach to evaluate the potential of the debonding distress in asphalt pavements

The debonding distress in asphalt pavement structures is a critical problem that affects the performance of asphalt concrete pavements. It occurs at the layer interface due to the poor bond quality between adjacent asphalt concrete layers and/or when stresses at the layer interface exceed the strengths of the material at the interface. The debonding of the adjacent layers, especially the top surface layer of an asphalt pavement, is a contributing factor to the premature cracking of pavements. Hence, the debonding distress can lead to a reduction in the life of the pavement. This paper presents an analytical and experimental framework to evaluate the potential for debonding at the layer interface of asphalt concrete pavements. Computational analysis was performed to determine the critical stress and strain states in layered asphalt pavements under moving vehicle loads using the Layered ViscoElastic pavement analysis for Critical Distresses (LVECD) computer program developed at North Carolina State University. This computational analysis enables a greater understanding of the critical stress that is involved in debonding and the ways that such stress is affected by pavement design parameters and environmental conditions. In addition, a prediction model was developed that can determine the shear bond strength at the interface of asphalt concrete layers with different tack coat materials at various temperatures, loading rates and normal confining stresses. The systematic and mechanistic framework developed in this study employs the maximum shear ratio concept as a shear failure criterion and provides a tool to evaluate the effects of various loading, environmental and pavement factors on the debonding potential of asphalt pavements. The overall advantages of the mechanistic framework and approach using the LVECD analysis tool will help lead to better understanding of the debonding mechanism, proper selection of the tack coats, and economic benefit in highway pavement maintenance and rehabilitation costs.     

Polyethylene Glycol–CaCl2 Coordination Compounds as a Novel Form‐Stable Phase Change Material with Excellent Thermophysical Properties

Polyethylene glycols (PEGs) have been extensively studied as phase change materials (PCMs). To overcome the problem of liquid leakage, the authors firstly report a novel form‐stable phase change material (FSPCM) using coordination compound. The structure, morphology, thermal property, and thermal stability of the self‐prepared samples are determined. The obtained results confirm the existence of coordination bonds between PEG and Ca²⁺ species, and no liquid leakage is observed for the synthesized PEG–CaCl₂ composites at temperatures as high as 120 °C. The PEG8000–CaCl₂ (1:2) FSPCM exhibits a relatively large latent heat of 147.7 J g^?1, corresponding to 87.8% of that of pure PEG. From the dynamical viewpoint, the activation energy of crystallization process is increased by only 5.2% for the PEG8000–CaCl₂ composite due to the formation of coordination bonds; however, the activation energy is reduced by 18.3% during melting process. After adding 3 wt% conductive carbon black, the heat storage performance of the PEG phase change material can be optimized. The PEG‐CaCl₂ composite would be a promising material for thermal energy storage applications and can be used in various engineering fields.

     

Selective Nanoscale Fabrication with Roughness Reduction of Polycrystalline Silicon by Physically Induced Fluorine Bonds Using Atomic Force Microscope

Polycrystalline silicon (poly-Si) is widely used as a gate layer in integrated circuits, transistors, and channels through nanofabrication. Nanoremoval and roughness control are required for nanomanufacturing of various electronic devices. Herein, a nanoscale removal method is developed to overcome the limitations of microcracks, complex procedures, and time-consuming conventional fabrication and lithography methods. The method is implemented with a mechanically induced poly-Si phase transition using atomic force microscope (AFM). Mechanical force induces the covalent bonds between silicon and fluorine atoms which cause the phase transition of poly-Si. Then, the bond structure of the Si molecules is weakened and selectively removed by nano-Newton-scale force using AFM. A selective nanoscale removal with roughness control is implemented in 0.5 mM TBAF solution after mechanical force (43.58–58.21 nN) is applied. By the magnitude of nano-Newton force, the removal depth of poly-Si is controlled from 2.66 to 21.52 nm. Finally, the nanoscale fabrication on poly-Si wafer is achieved. The proposed nanoremoval mechanism is a simple fabrication method that provides selective, nanoscale, and highly efficient removal with roughness control.     

Application of the independent molecule model to elucidate the dynamics of structure I methane hydrate: a second report

Two model systems of methane hydrate are constructed. One has a small cage surrounded by 12 large cages. The other has a large cage surrounded by four small cages and ten large cages. Three different H-bonding network patterns between waters are formed, and three random configurations of methane in each cage are chosen. A new method called the surface water fixed model is presented in which the energy minimum conformations for both model systems are preserved close to the X-ray crystallized structure. With normal mode analysis, we calculated frequencies of 2916.6 cm⁻¹ for a small cage at a centre, 2915.9 cm⁻¹ not at a centre, and 2911.7 cm⁻¹ for a large cage at a centre, and 2911.3 cm⁻¹ not at a centre. These frequencies are in moderate agreement with the corresponding Raman spectra, though not adequate. With our new method, however, it should be possible to improve agreement with the Raman spectra, if a model system vastly larger than the present model systems were constructed.     

共价键长的变化规律及计算

研究了共坐键长的变化规律,提出了两个影响键长的参数,即配位体的半径与中心原子半径之比Rraio和由中心原子组成的基团拓扑指数F2,用BP神经网络法,逼近了50个、预测了11个简单无机分子中非含氢原子键的键长,其计算误差基本上在2pm以内。     

Ion-cyclotron resonance study of elementary stages of the catalytic oxidation of CO by N2O in the presence of VIA-group metal ions

Gas phase reactions of Mo⁺ and W⁺ ions with the molecules of various oxidants (NO, O₂, N₂O, CH₂O, C₂H₄O) were studied using ion cyclotron resonance. In oxidation with N₂O the mono-, di- and trioxide metal cations are formed consecutively. The trioxide MO₃ ⁺ ions of both metals react with CO to form CO₂ and MO₂ ⁺ ions. In this way, catalytic reaction N₂O + CO N₂ + CO₂ occurs in the gas phase with MoO₃ ⁺ /MoO₂ ⁺ and WO₃ ⁺/WO₂ ⁺ couples as catalysts. The rate constants have been measured for both stages of the catalytic cycle as well as for the stages of the catalyst preparation. Metal-oxygen bond energies were estimated for MoO_x ⁺ and WO_x ⁺ species with various x. The mechanism of CO oxidation with MoO_x ⁺ and WO_x ⁺ cations as catalysts in the gas phase is discussed in comparison with that for the oxidation over classical solid oxide catalysts.     

国债市场的流动性套利及其实证检验

提出了一种在保持一定流动性风险的情况下构建国债套利组合的方法,应用线性规划技术,将国债的持有期风险因素引入到约束条件中,进而求解出实现最大期初套利的国债投资组合。通过对我国上交所25种债券的实证检验,发现套利收益与组合的持有期风险成正比,与流动性指标成反比,这证明了在考虑债券流动性风险的情况下,进行债券套利操作不一定会带来可观的收益。