Concentration fluctuation caused by reaction-diffusion coupling near catalytic active sites

The coupling of reaction and diffusion between neighboring active sites in the catalyst pore leads to the spatiotemporal fluctuation in component concentration, which is very important to catalyst performance and hence its optimal design. Molecular dynamics simulation with hard-sphere and pseudo-particle modeling has previously revealed the non-stochastic concentration fluctuation of the reactant/product near isolated active site due to such coupling, using a simple model reaction of A → B in 2D pores. The topic is further developed in this work by studying the concentration fluctuation due to such coupling between neighboring active sites in 3D pores. Two 3D pore models containing an isolated active site and two adjacent active sites were constructed, respectively. For the isolated site, the concentration fluctuation intensifies for larger pores, but the product yield decreases, and for a given pore size, the product yield reaches a peak at a certain reactant concentration. For two neighboring sites, their distance (d) is found to have little effect on the reaction, but significant to the diffusion. For the same reaction competing at both sites, larger d leads to more efficient diffusion and better overall performance. However, for sequential reactions at the two sites, higher overall performance presents at a smaller d. The results should be helpful to the catalyst design and reaction control in the relevant processes.     

Directional separation of hydrogen-containing gas mixture by hydrate-membrane coupling method

Recovery of hydrogen (H₂) from H₂-containing gas mixtures has great significance for energy conservation, cost reduction and benefit increase. However, the common separation methods have the ubiquitous problem due to phase equilibrium principle and results in the conflict between H₂ concentration and H₂ recovery rate in the product gas. Consequently, an innovative conception of hydrate-membrane coupling approach is proposed in this work. In the separation process, hydration and membrane permeation two separation driving forces coexist to achieve the aim of strengthening mass transfer kinetics. H₂ and non-H₂ components (hydrocarbons) are synchronously and directionally selected by membrane and hydrate to improve different phase compositions. Therefore, the gas in feed side could keep relatively high two separation driving forces (H₂ fugacity and hydrocarbons fugacity). The results show that the coupling method could synchronously increase both the concentration and the recovery rate of H₂ in the product gas. At the same time, the volume and concentration of the hydrocarbons in hydrate both increases effectively. It indicates that hydrate and membrane separation methods support each other in the separation process. The hydrate-membrane coupling method fundamentally solves the issue of the decreasing driving force resulting from single separation method and phase equilibrium relationship.     

高职模具类人才培养新模式的研究与实践

为了解决传统教学无法全面培养人才的问题,采用"课程融合+时空耦合+过程结合"的方式开展人才培养研究。以注射模设计与制造生产过程为导向,构建大项目牵引下的跨越课程、跨越学期的课程融合新模式,利用信息通信技术及互联网平台,将互联网与传统教学进行深度融合,创造新的教学生态,构建多元多维互动的时空耦合教学新关系,以全方位评价为引导,构建课程多元多维的评价新机制。以3个班级为对象开展不同模式下的教学,对试验班级成绩进行分析,研究结果表明:课程融合+时空耦合+过程结合新模式培养的学生更好地完成了综合项目,获得了较好的教学效果。     

Understanding δ-Bi2O3 fluorite degradation mechanism and related solutions for promising applications in distributed multigeneration

Oxygen selective membrane on the base of cermet δ-Bi₂O₃/Ag with an interpenetrating structure has the maximum potential efficiency of air separation. However, the degradation processes, including the phase degradation of fluorite δ-Bi₂O₃, do not make it possible to create a membrane with the required perfection and durability. In this work, the ordering of oxygen vacancies with the transformation of fluorite into the rhombohedral phase (S.G. R-3) was studied by powder HT XRD in situ at 600 °C on dense Bi_0.78Er_0.2Hf_0.02O_1.51 ceramics. Fast regeneration of disordered fluorite occurs at T = 640–700 °C. The phase degradation of fluorite due to the segregation of dopants at the second stage leads into stable phases - sillenite, tetragonal or rhombohedral phase (S.G. R-3m), depending on the composition of δ-Bi₂O₃. Fast regeneration of fluorite occurs when heated to 820 °C, which is unacceptable for membranes. Analysis of all available data allows us to propose approaches to optimize the composition of δ-Bi₂O₃ and technical solutions for creating durable oxygen selective membranes with promising use in distributed multigeneration. As a result of the analysis, a new solid electrolyte with better parameters was obtained.     

Fe3O4-carbon spheres core–shell supported palladium nanoparticles: A robust and recyclable catalyst for suzuki coupling reaction

Suzuki-Miyaura (S-M) is regarded the most powerful way for synthesis biaryls, triaryls, or incorporating of substituted aryl moieties in organic preparation by the cross-coupling of aryl boronic acid with aryl halides using the Pd catalyst. This work reports the combining of the hydrothermal and microwave-assisted protocol to convert the glucose to magnetic carbon spheres (Fe₃O₄-CSPs) decorated with Pd nanoparticles (NPs) as the catalyst for Suzuki-Miyaura cross-coupling reactions. The physicochemical properties in the produced composite were examined using FESEM, HRTEM, nitrogen isotherms, Raman spectroscopy, FTIR, XPS, and XRD. The as-fabricated composite Pd/Fe₃O₄-CSPs is mostly spherical with a core–shell structure and possesses a great surface area of 253.2 m²·g^-1. Its catalytic performance demonstrates that the composite has excellent stability and high tolerance Suzuki-Miyaura cross-coupling reactions in 30 min at 80 ℃. Both activated and deactivated aryl halides provided excellent yield. The as-fabricated catalyst was recycled for up to four catalytic cycles without a substantial decline in performance. Moreover, this research offers a facile roadmap for synthesizing Pd/Fe₃O₄-CSPs composites and promoting the practical implementation of Pd/Fe₃O₄-CSPs catalysts for organic transformation processes.     

Synthesis of thermoresponsive copolymer/silica-coated magnetite nanoparticle composite and its application for heavy metal ion recovery

To enhance chemical stability and suppress of aggregation of magnetite nanoparticles (MNPs), which are used as a support for thermoresponsive copolymer immobilization, silica coating of the MNPs is applied via the electrooxidation method. Although the resulting silica coated-MNPs also formed aggregates, the size distribution of the aggregate shifted to smaller size range. Because of that, the surface area available for copolymer immobilization increased approximately 6.7 times at maximum as compared with that of the uncoated MNPs. It contributed to the increase of the amount of the immobilized copolymer on the silica-coated MNPs, which is approximately four times larger than that on the uncoated MNPs. Fe₃O₄ dissolution test confirmed enhancement of chemical stability of MNPs. The thermoresponsive copolymer immobilized on the silica-coated MNPs shows the ability to recycle Cu(II) ion from Cu(II) containing solution by changing temperature with significantly shorter time than those in other thermoresponsive adsorbents in gel form.     

Soluble network polymers based on trifluoropropyl-substituted open-cage silsesquioxane: Synthesis,properties, and application for surface modifiers

Fluorinated completely condensed polyhedral oligomeric silsesquioxanes (F-CC-POSSs) are widely utilized as surface modifiers for polymeric materials because of their polyhedral and fluorine-rich structures, which generate polymers with lower surface energies under molecular-level control. In contrast, their derivatives, fluorinated incompletely condensed or open-cage POSSs (F-IC-POSSs), have similarly intriguing structures, but their utilization for polymer synthesis remains undeveloped. Herein, fluorinated network polymers were prepared based on a 3,3,3-trifluoropropyl-substituted IC-POSSs via hydrosilylation polymerization with isobutyl- and phenyl-substituted IC-POSS under optimized conditions. In addition to their good thermal stability and tunable refractive indices, these polymers exhibited solution processability and their casting films showed excellent optical transparency, indicating their potential for constructing fluorinated polymers. Their utilization as surface modifiers was examined by addition to poly(methylmethacrylate) (PMMA) films. Intriguingly, modified PMMA films with 2.0 and 0.5 wt% addition showed similar hydrophobicity and surface energies to the films prepared with only fluorinated network polymers.     

导管架平台上部组块双船拆除

为研究复杂海域环境中海洋平台双船拆除方法的安全性与可操作性,采用水动力数值计算与水池模型试验相结合的方法进行研究。将双船水动力耦合计算与水池模型试验进行对比,在相对理想海况下,结合与实际工况接近的规则波作用,进行驳船水动力性能变化与运动响应的幅值分析。在受力分析方面,对甲板耦合装置进行改良设计,对比试验数据与数值计算数据,得到受力在合理范围内的结论。研究内容为实际施工的合理性提出一定的指导性意见。     

Effect of particle grading on fracture behavior and thermal shock resistance of MgO-C refractories

Two types of MgO-C refractories with tight particle grading and non-tight particle grading were prepared according to Andreasen's continuous packing theory. Fracture behaviors were investigated using wedge splitting tests combined with digital image correlation method and acoustic emission techniques. The results indicated that MgO-C refractory with non-tight particle grading treated at 1400 ℃ had more in situ phases (e.g., AlN and MgAl₂O₄) and exhibited less brittleness than specimens with tight particle grading even though they had similar nominal tensile strengths. In contrast, specimens with non-tight particle grading had greater horizontal strain under various loading stages, reflecting their better ability to resist rupture deformation. In addition, more microcracks were initiated earlier in the pre-peak region, and more energy was consumed. The decrease in coarse particles and corresponding increase in fine powder content increased the interface between particles, benefiting for reducing the local stress concentration and improving the thermal shock resistance of refractories.     

Magnetodielectric coupling in barium titanate–cobalt ferrite composites obtained via thermally-assisted high-energy ball milling

In this work, a magnetodielectric coupling observed in barium titanate–cobalt ferrite composites synthesized using high-energy ball milling assisted via a thermal treatment is discussed. Vibrating sample magnetometry and dielectric spectroscopy showed that multiferroic composites possess both ferromagnetic and dielectric behaviors inherited from the parent ferromagnetic cobalt ferrite and ferroelectric barium titanate phases. The magnetocapacitance (up to 35%) recorded for x = 0.3, (1-x)BaTiO₃–xCoFe₂O₄, can be attributed to the spin-dependent filtering mechanism. The composite with the aforementioned composition exhibited a homogeneous matrix–particle composite microstructure, which was achieved via high-energy ball milling during the mixing stage.