CeO2复合改性ZSM-5分子筛用于催化甲醇制丙烯研究

在甲醇制丙烯(MTP)反应中,ZSM-5分子筛较强的酸性易使甲醇与ZSM-5接触发生氢转移、芳构化等二次反应,堵塞孔道,使得其微孔结构更加不利于分子的扩散,加速催化剂积碳失活,导致丙烯选择性和丙烯/乙烯(P/E)比值下降。因此,本文利用催化活性较高的CeO₂对ZSM-5分子筛进行复合改性以达到有效降低其酸性并增大介孔的目的来提高丙烯选择性和P/E比。通过XRD、NH₃-TPD和N₂吸脱附技术表征,研究了不同ZSM-5硅铝比(摩尔比)、两相质量比(m(CeO₂)/m(ZSM-5))对CeO₂/ZSM-5复合催化剂物化性质的影响。在反应温度480 ℃、重时空速2.6 h^-1、N₂流量100 mL·min^-1、常压纯甲醇进料的条件下,考察了所制备的复合催化剂催化MTP的性能。结果表明,硅铝比为250、m(CeO₂)/m(ZSM-5)为1∶4的复合催化剂比以往研究结果具有更优异的MTP催化性能,甲醇转化率为99.9%,丙烯选择性为42.78%,P/E比为6.3。     

制冷剂充注量对微通道蒸发器换热性能影响的实验研究

以微通道换热器作为柜式空调蒸发器,设计并加工了微通道蒸发器(MCE,扁管和翅片均为铝材),搭建实验测试系统。研究了三种入口形式(Z-Inlet, Y-Inlet, U-Inlet)、五种制冷剂充注量(800~1600 g)下微通道蒸发器的表面温度分布、制冷量(Q)、输入功率(Pin)和能效比(EER),并与管翅式换热器(FTE,铜管-铝翅片)进行对比分析。结果表明,Z-Inlet形式MCE内部制冷剂行程基本相同,流量分配较均匀,其表面温度分布比较均匀,换热效果最佳;Z-Inlet形式MCE的制冷量和EER最高,与另外两种形式相比,制冷量和EER最高分别提高了8.8%和5.7%;MCE的制冷量和EER比FTE大,制冷量平均超出了11%,最高达13.3% (约600 W),EER平均提升了9.36%,最大约为12.4%;此外MCE的EER达到峰值对应的制冷剂充注量与FTE相比减少了200 g。     

Effects of Y2O3/MgO ratio on mechanical properties and thermal conductivity of silicon nitride ceramics

In this work, the effects of Y₂O₃/MgO ratio on the densification behavior, phase transformation, microstructure evolution, mechanical properties, and thermal conductivity of Si₃N₄ ceramics were investigated. Densified samples with bimodal microstructure could be obtained by adjusting the ratio of Y₂O₃/MgO. It was found that a low Y₂O₃/MgO ratio facilitated the densification of Si₃N₄ ceramics while a high Y₂O₃/MgO ratio benefited the phase transformation of Si₃N₄ ceramics. Best mechanical properties (flexural strength of 875 MPa, and fracture toughness of 8.25 MPa·m^1/2, respectively) and optimal thermal conductivity of 98.04W/(m·K) were achieved in the sample fabricated with Y₂O₃/MgO ratio of 3:4 by sintering at 1900°C for 4 h.     

Photocatalytic degradation of Basic Blue 41 dye under visible light over SrTiO3/Ag3PO4 hetero-nanostructures

In an attempt to develop nanostructured photocatalysts with high performance, SrTiO₃/Ag₃PO₄ hetero-nanostructures were successfully fabricated. The formed binary heterojunctions were composed of SrTiO₃ nanotubes prepared using liquid-phase deposition, and Ag₃PO₄ nanoparticles prepared using a sol–gel method. Synthesis details, including morphology, structure, and optical properties of the prepared photocatalysts, were characterized and comparatively discussed. The results showed that at an optimal ratio of SrTiO₃ to Ag₃PO₄ (20–80), the photocatalytic degradation of Basic Blue 41 under 80-min visible light irradiation is the maximum amount of 99%, which is about 4.4 and 1.5 times higher than that of pristine SrTiO₃ nanorods and Ag₃PO₄ nanoparticles, respectively. It can be due to the synergistic effect of two materials that provide high light absorption and charge carriers’ separation. Finally, a detailed possible mechanism for enhancing the photocatalytic activity of the SrTiO₃/Ag₃PO₄ hetero-nanostructures was proposed.     

Genomic and metabolomic analysis of Bacillus licheniformis with enhanced poly-γ-glutamic acid production through atmospheric and room temperature plasma mutagenesis

Poly-γ-glutamic acid is an extracellular polymeric substance with various applications owing to its valuable properties of biodegradability, flocculating activity, water solubility, and nontoxicity. However, the ability of natural strains to produce poly-γ-glutamic acid is low. Atmospheric and room temperature plasma was applied in this study to conduct mutation breeding of Bacillus licheniformis CGMCC 2876, and a mutant strain M32 with an 11% increase in poly-γ-glutamic acid was obtained. Genome resequencing analysis identified 7 nonsynonymous mutations of ppsC encoding lipopeptide synthetase associated with poly-γ-glutamic acid metabolic pathways. From molecular docking, more binding sites and higher binding energy were speculated between the mutated plipastatin synthase subunit C and glutamate, which might contribute to the higher poly-γ-glutamic acid production. Moreover, the metabolic mechanism analysis revealed that the upregulated amino acids of M32 provided substrates for glutamate and promoted the conversion between L- and D-glutamate acids. In addition, the glycolytic pathway is enhanced, leading to a better capacity for using glucose. The maximum poly-γ-glutamic acid yield of 14.08 g·L^–1 was finally reached with 30 g·L^–1 glutamate.     

Room-temperature hydrogenation of halogenated nitrobenzenes over metal–organic-framework-derived ultra-dispersed Ni stabilized by N-doped carbon nanoneedles

Ultra-dispersed Ni nanoparticles (7.5 nm) on nitrogen-doped carbon nanoneedles (Ni@NCNs) were prepared by simple pyrolysis of Ni-based metal–organic-framework for selective hydrogenation of halogenated nitrobenzenes to corresponding anilines. Two different crystallization methods (stirring and static) were compared and the optimal pyrolysis temperature was explored. Ni@NCNs were systematically characterized by wide analytical techniques. In the hydrogenation of p-chloronitrobenzene, Ni@NCNs-600 (pyrolyzed at 600 °C) exhibited extraordinarily high performance with 77.9 h^–1 catalytic productivity and > 99% p-chloroaniline selectivity at full p-chloronitrobenzene conversion under mild conditions (90 °C, 1.5 MPa H₂), showing obvious superiority compared with reported Ni-based catalysts. Notably, the reaction smoothly proceeded at room temperature with full conversion and > 99% selectivity. Moreover, Ni@NCNs-600 afforded good tolerance to various nitroarenes substituted by sensitive groups (halogen, nitrile, keto, carboxylic, etc.), and could be easily recycled by magnetic separation and reused for 5 times without deactivation. The adsorption tests showed that the preferential adsorption of –NO₂ on the catalyst can restrain the dehalogenation of p-chloronitrobenzene, thus achieving high p-chloroaniline selectivity. While the high activity can be attributed to high Ni dispersion, special morphology, and rich pore structure of the catalyst.     

Diffusion process in enzyme–metal hybrid catalysts

Enzyme–metal hybrid catalysts bridge the gap between enzymatic and heterogeneous catalysis, which is significant for expanding biocatalysis to a broader scope. Previous studies have demonstrated that the enzyme–metal hybrid catalysts exhibited considerably higher catalytic efficiency in cascade reactions, compared with that of the combination of separated enzyme and metal catalysts. However, the precise mechanism of this phenomenon remains unclear. Here, we investigated the diffusion process in enzyme–metal hybrid catalysts using Pd/lipase-Pluronic conjugates and the combination of immobilized lipase (Novozyme 435) and Pd/C as models. With reference to experimental data in previous studies, the Weisz–Prater parameter and efficiency factor of internal diffusion were calculated to evaluate the internal diffusion limitations in these catalysts. Thereafter, a kinetic model was developed and fitted to describe the proximity effect in hybrid catalysts. Results indicated that the enhanced catalytic efficiency of hybrid catalysts may arise from the decreased internal diffusion limitation, size effect of Pd clusters and proximity of the enzyme and metal active sites, which provides a theoretical foundation for the rational design of enzyme–metal hybrid catalysts.     

Nickel-based metal−organic framework-derived whisker-shaped nickel phyllosilicate toward efficiently enhanced mechanical,flammable and tribological properties of epoxy nanocomposites

Metal−organic framework-derived materials have attracted significant attention in the applications of functional materials. In this work, the rod-like nickel-based metal−organic frameworks were first synthesized and subsequently employed as the hard templates and nickel sources to prepare the whisker-shaped nickel phyllosilicate using a facile hydrothermal technology. Then, the nickel phyllosilicate whiskers were evaluated to enhance the mechanical, thermal, flammable, and tribological properties of epoxy resin. The results show that adequate nickel phyllosilicate whiskers can disperse well in the matrix, improving the tensile strength and elastic modulus by 13.6% and 56.4%, respectively. Although the addition of nickel phyllosilicate whiskers could not obtain any UL-94 ratings, it enhanced the difficulty in burning the resulted epoxy resin nanocomposites and considerably enhanced thermal stabilities. Additionally, it was demonstrated that such nickel phyllosilicate whiskers preferred to improve the wear resistance instead of the antifriction feature. Moreover, the wear rate of epoxy resin nanocomposites was reduced significantly by 80% for pure epoxy resin by adding 1 phr whiskers. The as-prepared nickel phyllosilicate whiskers proved to be promising reinforcements in preparing of high-performance epoxy resin nanocomposites.     

A density functional theory study of methane activation on MgO supported Ni9M1 cluster: role of M on C–H activation

Methane activation is a pivotal step in the application of natural gas converting into high-value added chemicals via methane steam/dry reforming reactions. Ni element was found to be the most widely used catalyst. In present work, methane activation on MgO supported Ni–M (M = Fe, Co, Cu, Pd, Pt) cluster was explored through detailed density functional theory calculations, compared to pure Ni cluster. CH₄ adsorption on Cu promoted Ni cluster requires overcoming an energy of 0.07 eV, indicating that it is slightly endothermic and unfavored to occur, while the adsorption energies of other promoters M (M = Fe, Co, Pd and Pt) are all higher than that of pure Ni cluster. The role of M on the first C–H bond cleavage of CH₄ was investigated. Doping elements of the same period in Ni cluster, such as Fe, Co and Cu, for C–H bond activation follows the trend of the decrease of metal atom radius. As a result, Ni–Fe shows the best ability for C–H bond cleavage. In addition, doping the elements of the same family, like Pd and Pt, for CH₄ activation is according to the increase of metal atom radius. Consequently, C–H bond activation demands a lower energy barrier on Ni–Pt cluster. To illustrate the adsorptive dissociation behaviors of CH₄ at different Ni–M clusters, the Mulliken atomic charge was analyzed. In general, the electron gain of CH₄ binding at different Ni–M clusters follows the sequence of Ni–Cu (–0.02 e) < Ni (–0.04 e) < Ni–Pd (–0.08 e) < Ni–Pt (–0.09 e) < Ni–Co (–0.10 e) < Ni–Fe (–0.12 e), and the binding strength between catalysts and CH ₄ raises with the CH₄ electron gain increasing. This work provides insights into understanding the role of promoter metal M on thermal-catalytic activation of CH₄ over Ni/MgO catalysts, and is useful to interpret the reaction at an atomic scale.