Copper‐Catalyzed Difunctionalization of Activated Alkynes by Radical Oxidation–Tandem Cyclization/Dearomatization to Synthesize 3‐Trifluoromethyl Spiro[4.5]trienones

A copper‐catalyzed difunctionalizing trifluoromethylation of activated alkynes with the cheap reagent sodium trifluoromethanesulfinate (NaSO₂CF₃ or Langlois’ reagent) has been developed incorporating a tandem cyclization/dearomatization process. This strategy affords a straightforward route to synthesis of 3‐(trifluoromethyl)‐spiro[4.5]trienones, and presents an example of difunctionalization of alkynes for simultaneous formation of two carbon–carbon single bonds and one carbon–oxygen double bond.     

航空导管弯曲试验的疲劳裂纹萌生寿命

飞行器液压导管受接头和卡箍等约束，在使用的振动环境中，会因弯曲应力而导致破裂，影响到飞行安全．本文对飞行器液压系统通用的不锈钢导管的裂纹萌生寿命进行了试验研究．首先在对8 mm、12 mm 无缺陷导管和含U 型缺口8 mm 导管的疲劳试验和有限元分析的基础上，得到了导管的最大拉应变-裂纹萌生寿命数据．然后采用基于强度极限和弹性模量估算法的Manson-Coffin 公式来预测导管裂纹萌生寿命．最后引入加载类型修正系数、表面质量修正系数、试样尺寸修正系数、应力集中敏感系数和有效应力集中系数，使修正后的公式对三种类型的导管均有较好的裂纹萌生寿命预测精度．     

Metal-Mediated Directional Capping of Rod-Packing Metal–Organic Frameworks

Two new rod-packing metal–organic frameworks (RPMOF) are constructed by regulating the in situ formation of the capping agent. In CPM-s7, carboxylate linkers extend 1D manganese-oxide chains in four additional directions, forming 3D RPMOF. The substitution of Mn²⁺ with a stronger Lewis acidic Co²⁺, leads to an acceleration of the hydrolysis-prone sulfonate linker, resulting in presence of sulfate ions to reduce two out of the four carboxylate-extending directions, and thus forming a new 2D rod-packing CPM-s8. Density functional theory calculations and magnetization measurements reveal ferrimagnetic ordering of CPM-s8, signifying the potential of exploring 2D RPMOF for effective low-dimensional magnetic materials.     

The Spin Modulation Stimulated Efficient Electrocatalytic Oxygen Evolution Reaction over LaCoO3 Perovskite

Perovskite is a promising non-noble catalyst and has been widely investigated for the electrochemical oxygen evolution reaction (OER). However, there is still serious lack of valid approaches to further enhance their catalytic performance. Herein, we propose a spin state modulation strategy to improve the OER electrocatalytic activity of typical perovskite material of LaCoO₃. Specifically, the electronic configuration transition was realized by a simple high temperature thermal reduction process. M-H hysteresis loop results reveal that the reduction treatment can produce more unpaired electrons in 3d orbit by promoting the electron transitions of Co from low spin state to high spin state, and thus lead to the increase of the spin polarization. Electrochemical measurements show that the catalytic performance of LaCoO₃ is strongly dependent on its electronic configuration. With the optimized reduction treatment, the overpotential for the OER process in 0.5 M KOH electrolyte solution at 10 mA cm⁻² current density was 396 mV, significantly lower than that of the original state. Furthermore, it can mediate efficient OER with an overpotential of 383 mV under an external magnetic field, which is attributed to the appropriate electron filling. Our results show that electron spin state regulation is a new way to boost the OER electrocatalytic activity.     

Electro-assisted Molecular Assembly Giving Atomic-Scale Catalytic Active-Site Detection

The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro-assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon-defect electrocatalysis reaction mechanism was first downsized to the single-atom scale from the experimental perspective. It is expected that this innovative electro-assisted molecular assembly strategy could be extensively applied in the active structure-controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom.     

枝晶生长理论中的热-动力学协同

随加工工艺趋于复杂化和极端化,基于热力学驱动力和动力学能垒相对独立的枝晶生长理论已无法精确描述多种机制共同作用的非平衡凝固过程,大大限制了该理论与工业应用的结合。首先,本文综述基于热-动力学相对独立的枝晶生长理论的发展,分析其内涵的本征热-动力学相关性,并集成于以双辊薄带连铸技术为背景的基于热-动力学相关性的枝晶生长模型。其次,定量证明了热力学驱动力和动力学能垒的相关性,通过选择不同的驱动力-能垒组合,试图在双辊薄带连铸技术中实现合金设计和工艺优化。最后,通过分析现有模型的不足,对进一步枝晶生长模型的发展以及与工艺的结合进行展望。     

低温固相反应法制备钠快离子导体NaZr2(PO4)3粉体

为了进一步促进钠快离子导体磷酸锆钠(NaZr2(PO4)3)粉体的实际应用,本文提出了一种以氧氯化锆(ZrOCl2·8H2O)和二水磷酸二氢钠(NaH2PO4·2H2O)为原料的低温固相反应法制备NaZr2(PO4)3粉体.通过XRD,SEM和Raman等测试手段系统研究了磷酸盐用量对制备磷酸锆钠粉体的影响.结果 表明:采用超量的磷酸盐有利于纯相磷酸锆钠粉体的合成.同时当锆盐与磷酸盐的摩尔比为2∶5.4时,能够合成平均粒径1μm,尺寸均匀,分散性良好的磷酸锆钠粉体.研究发现研磨时发生的固相反应对磷酸锆钠粉体的制备有重要作用,一方面促进了无定型磷酸锆钠的产生,有利于磷酸锆钠晶体形成;另一方面原位生成的氯化钠为晶体的生长提供了良好的液相环境,促进了磷酸锆钠粉体的低温合成.该工作为磷酸锆钠粉体的大规模生产提供了一条简单有效的方法.