Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.     

基于内聚力模型的快速荷载下CFRP-混凝土界面剪切剥离模拟

鉴于纤维增强复合材料(Fiber Reinforced Polymer, FRP)已在混凝土结构加固中普遍应用, 能有效提高结构的承载和变形能力. 为揭示动载作用下FRP-混凝土界面的剥离机理, 本文基于ABAQUS平台, 采用内聚力模型模拟CFRP-混凝土界面层, 实现了快速荷载下CFRP-混凝土界面剥离的高效模拟. 结果表明: CFRP表面应变在加载过程中由加载端向自由端方向传递, 随着加载速率的提高, 界面承载能力也随之提高; 界面峰值剪应力也存在显著的应变率效应; 模拟结果与试验结果基本吻合, 说明了新方法的有效性.     

货运动车组装载门凹陷对隧道内会车压力波的影响

随着我国技术经济水平的提高，电子商务产业快速发展，货运动车组应运而生。采用有限体积方法和重叠网格方法，以及SST k-ω高雷诺数湍流模型，数值模拟研究时速350 km的货运动车组在隧道内交会的压力波，探究货运动车组车体结构即装载门凹陷对隧道内交会压力波的影响。实车试验结果验证了本文数值模拟方法的准确性。研究结果表明，凹陷的装载门使平直车身处的最大正压值增大约20%~30%，且有无凹陷的装载门中心最大正压值的差异百分比维持在35%~80%，最大负压值差异百分比在20%~25%。     

内部爆炸作用下多层钢筒的动态响应

为评估内部爆炸作用下多层钢筒结构的防护效果，考察多层钢筒结构动态响应和变形吸能特征，采用两端开口、总厚度为50 mm的4层圆柱形Q345钢筒，在8.90~18.18 kg TNT药量下进行爆炸实验，并在容器外壁进行应变电测。实验后钢筒结构爆心局部发生塑性变形，内层钢筒变形最大，但未发生破坏。根据研究得到初步认识:采用爆心单位环面变形吸能的设计方法，可以较好地预估给定药量下所需钢筒的厚度；不同药量下，轴向距离超过多层钢筒结构的1/4内径后，其外壁环向变形峰值约减小为爆心截面环向应变峰值的1/2。     

实现应变率为105~106 s-1的阻抗梯度飞片复杂加载波形计算分析

为了在气炮上实现应变率为105~106 s-1的复杂加载技术研究，采用自行研制的拉格朗日程序MLEP(multi-material Lagrangian elastic-plastic)对Al-Cu-W材料体系的阻抗梯度飞片复杂加载不锈钢靶板进行数值模拟，计算设计并分析了阻抗梯度飞片的厚度和密度分布指数对靶板压力、速度和应变率峰值等波形的影响。结果表明:密度指数分布越大，加载时间越短，加载后期的压力、速度和应变率峰值曲线更陡峭；同时, 为了避免靶板/LiF窗口界面反射的稀疏波早于阻抗梯度飞片后界面反射的稀疏波达到碰撞面位置，计算设计中还考虑了飞片厚度的影响。此外，对基于理论设计的阻抗梯度飞片进行了动态考核实验，实验结果基本反映了预期的设计，为材料强度的测量奠定了基础。     

Rate sensitivity and deformation mechanism of semi-crystalline polymers during instrumented indentation

Instrumented indentation tests using both constant loading rate (CLR) and continuous stiffness measurement (CSM) operation modes were performed to investigate the deformation mechanism and their sensitivity to the deformation rate in semi-crystalline polymers through the quantitative analysis of load-depth loading and unloading curves. The strain rate was constant during the CSM tests, while the strain rate decreased with the increasing of loading time in CLR tests. The mechanical response mechanism of the semi-crystalline polymers to these tests was very complicated because of the combined effects of strain-hardening in the crystal phase and strain-softening in the amorphous phase. Results show that the loading index m reflects the strain-hardening or strain-softening response during indentation. When m > 2, the mechanical response was due to the strain-hardening, and when m < 2, the response was due to strain-softening. A method based on the measured contact hardness was proposed to obtain the unloading stiffness, and the other mechanical parameters could then be determined according to the unloading stiffness.     

Thermally Crosslinkable and Chemically Modifiable Aromatic Polyesters Possessing Pendant Propargyloxy Groups

New aromatic (co)polyesters containing pendant propargyloxy groups were synthesized by phase transfer‐catalyzed interfacial polycondensation of 5‐(propargyloxy)isophthaloyl chloride (P‐IPC) and various compositions of P‐IPC and isophthaloyl chloride with bisphenol A. FTIR and NMR spectroscopic data, respectively, revealed successful incorporation of pendant propargyloxy groups into (co)polyesters and formation of (co)polyesters with desired compositions. (Co)polyesters exhibited good solubility in common organic solvents such as chloroform, dichloromethane, and tetrahydrofuran and could be cast into transparent, flexible, and tough films from chloroform solution. Inherent viscosities and number average molecular weights of (co)polyesters were in the range 0.77–1.33 dL/g and 43,600–118,000 g/mol, respectively, indicating the achievement of reasonably high‐molecular weights. The 10% weight loss temperatures of (co)polyesters were in the range 390–420 °C, demonstrating their good thermal stability. (Co)polyesters exhibited T_g in the range 146–170 °C and T_g values decreased with increase in mol % incorporation of P‐IPC. The study of non‐isothermal curing by DSC indicated thermal crosslinking of (co)polyesters via propargyloxy groups. The utility of pendant propargyloxy group was demonstrated by post‐modification of the selected copolyester with 1‐(4‐azidobutyl)pyrene, 9‐(azidomethyl)anthracene, and azido‐terminated poly(ethyleneglycol) monomethyl ether via copper(I)‐catalyzed Huisgen 1,3‐dipolar cycloaddition reaction. FTIR and ¹H NMR spectra confirmed that click reaction was quantitative. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 588–597     

锡负载量对PtSn/Al2O3催化丙烷脱氢性能的影响

采用羰基合成-浸渍法制备了不同Pt/Sn摩尔比(3:1, 1:1, 1:2和1:3)的PtSn/Al₂O₃催化剂, 利用N₂吸附-脱附实验、 X射线衍射(XRD)、 透射电子显微镜(TEM)、 吡啶吸附红外光谱(Py-IR)和热重-差热分析(TG-DTA)等手段对其进行了表征, 研究了Sn负载量对PtSn/Al₂O₃的结构性质及催化丙烷脱氢性能的影响. 结果表明, 制备的PtSn/Al₂O₃具有较高的丙烯选择性和稳定性. 当Pt/Sn摩尔比为3:1和1:1时, 铂和锡在催化剂上主要以Pt₃Sn和PtSn合金形式存在, 合金的形成明显改善了催化剂的脱氢性能, 可抑制金属颗粒的高温烧结; 当Pt/Sn摩尔比为1:2和1:3时, 铂主要以金属形式存在. 随着Sn负载量的增加, 催化剂上L酸性位逐渐减少, 丙烷转化率降低, 丙烯选择性增加, 同时促使反应积炭从金属表面向载体迁移, 改善了催化剂的稳定性.     

THE SHEAR LAG EFFECT OF BOX BEAMS WITH VARYING LATERAL LOADING LOCATIONS 1)

对箱梁各翼板(顶板、悬臂板、底板)分设不同剪力滞广义纵向位移,其横向分布均取二次抛物线形式,并引入载荷横向位置参数η,以分析载荷横向变位对剪力滞效应的影响.运用能量变分原理,建立剪力滞控制微分方程,求解了简支梁和悬臂梁在均布载荷作用下的控制微分方程的解.算例分析表明:载荷横向变位改变直接承受载荷的翼板的正负剪力滞特性,对非直接承载翼板只改变其应力幅度;箱梁横向框架效应对直接承载翼板纵向应力的贡献远远大于剪切变形.与块体有限元分析结果较吻合,表明该算法能较准确分析载荷横向变位作用下箱梁剪力滞的变化规律.     

闪长岩单轴加载过程中声发射和弹性波速度变化规律的研究

为研究闪长岩在单轴加载过程中的声发射和各向波速变化规律,在单轴阶段加载和循环阶段加载条件下,对闪长岩岩样破裂过程中的声发射累计数、不同应力水平不同方向的波速、切线模量、轴向应变速率进行了研究。实验结果表明:(1)随着应力水平的增高,声发射事件数不断增加,在高应力水平(约80%峰值强度)时,声发射累计数急剧增多,随后切线模量出现震荡变化。(2)在加载过程中,压密程度及裂纹扩展方向对波速产生了巨大的影响,导致不同方向波速在不同的应力水平呈现出不同的变化规律,由此可以推测破裂面位置和破裂模式。在较高应力水平下(约60%峰值强度),平行于加载方向的波速趋于稳定,而垂直于加载方向的波速则持续下降,故用垂直于加载方向传播的波速预测岩石的破坏更具可靠性。(3)随着应力的增加,应变速率有逐渐减小的趋势,但临近岩石破裂时无异常变化出现,说明利用变形观测难以预测此类岩石的破坏。以上研究表明,根据纵波波速、声发射累计数和切线模量的变化可以有效预测岩石的破坏。