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.     

双激光脉冲打靶形成Gd等离子体的极紫外光谱辐射

高端芯片制造所需要的极紫外光刻技术位于我国当前面临35项"卡脖子"关键核心技术之首.高转换效率的极紫外光源是极紫外光刻系统的重要组成部分.本文通过采用双激光脉冲打靶技术实现较强的6.7 nm极紫外光输出.首先,理论计算Gd¹⁸⁺—Gd²⁷⁺离子最外层4d壳层的4p-4d和4d-4f能级之间跃迁、以及Gd¹⁴⁺—Gd¹⁷⁺离子最外层4f壳层的4d-4f能级之间跃迁对波长为6.7 nm附近极紫外光的贡献.其后开展实验研究,结果表明,随着双脉冲之间延时的逐渐增加,波长为6.7 nm附近的极紫外光辐射强度呈现先减弱、后增加、之后再减弱的变化趋势,在双脉冲延时为100 ns处产生的极紫外光辐射最强.并且,在延时为100 ns处产生的光谱效率最高,相比于单脉冲激光产生的光谱效率提升了33%.此外,发现双激光脉冲打靶技术可以有效地减弱等离子体的自吸收效应,获得的6.7 nm附近极紫外光谱宽度均小于单激光脉冲打靶的情形,且在脉冲延时为30 ns时刻所产生的光谱宽度最窄,约为单独主脉冲产生极紫外光谱宽度的1/3.同时...     

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.     

通过超宽139La固体核磁共振波谱研究层状La(OH)2NO3

层状稀土氢氧化物是一类新型的稀土功能材料，本文采用固体核磁共振（SSNMR）方法研究了同时具备离子交换能力和非线性光学特性的层状La（OH）₂NO₃化合物，探讨了通过四极核CPMG（QCPMG）脉冲序列和变频谱图采集获取超宽¹³⁹La SSNMR谱图的方法，并描述了适用于此类实验的滤波方程和谱图重建方法.重建谱图同时包含四极核中心跃迁和卫星跃迁信息，本文使用QUEST软件对超宽¹³⁹La NMR谱图进行了模拟，获取的四极耦合常数C_Q和非对称因子η_Q均与CASTEP密度泛函理论计算值高度吻合.SSNMR实验结果证实层状La（OH）₂NO₃化合物属于非中心对称结构（P2₁），解决了对其结构长期以来存在的争论.     

三色圆偏振激光组合脉冲驱动氦原子产生椭圆偏振的阿秒脉冲

我们提出利用频率为ω,3ω和强度较弱的2ω组成的三色圆偏振激光组合脉冲驱动氦原子能够得到椭偏率较大的阿秒脉冲链的一种方法.通过强场近似方法,计算了氦原子在两色和三色圆偏振激光组合脉冲驱动下发射高次谐波谱及其合成阿秒脉冲链,比较了氦原子(初态为s态)在这两种情况下发射高次谐波谱的特点及其合成阿秒脉冲链椭偏率的大小,结果发现,在反旋的两色ω,3ω激光脉冲基础上加入了频率为2ω的第三色激光脉冲联合作用到氦原子上,所得到的阿秒脉冲链的椭偏率相对于双圆场情况下有所增加,通过调整ω,3ω激光的强度比,并且选择适当的第三色激光的强度,对初态为s态的原子,仍能够得到具有较大椭偏率的阿秒脉冲链.     

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.     

基于耦合Ginzburg-Landau方程的石墨烯锁模光纤激光器的暗暗孤子解及其稳定性

以耦合Ginzburg-Landau方程为模型,对石墨烯锁模光纤激光器中脉冲的动力学行为进行了详细地研究.首先,采用拟解法推导了该方程组的啁啾类暗暗孤子对解;其次,对啁啾类暗暗孤子对的传输特性及稳定性进行了数值研究.结果表明:合理选择系统参数,不仅可以得到啁啾类暗暗孤子对的精确解,而且该精确解还可以在一定的扰动下稳定传输.相关结果将为设计和改善石墨烯锁模光纤激光器的性能提供一定的理论依据.     

无序激光晶体及其超快激光研究进展

激光是受激辐射的光放大,所辐射的波长取决于增益介质中关键电子的能级结构,特别是其最外层电子的状态决定了可能实现的激光特性。激光发展60年来,激光晶体作为激光的重要激活材料,推动了激光技术的进步和普及,是一个研究历史长而又异常活跃的研究领域。当前,超短超强脉冲激光在加工、医疗、国防等关系国计民生的领域有重要需求,适合超短超强激光的激光晶体成为了本领域的研究热点,其关键是揭示最外层电子的影响因素及设计和生长具有宽波段发射性能的激光晶体。本论文从探讨影响激活离子光谱性能的关键因素出发,综述了以本课题组十余年研究的10余种无序激光晶体为主要部分的研究结果和进展,涉及晶体生长、晶体物理、激光器件设计及应用等工作,包含了高级、中级和低级对称性晶体及其获得的最短脉冲激光结果,希望能为本领域的后续研究提供一定的参考和借鉴。     

Flume testing of passively adaptive composite tidal turbine blades under combined wave and current loading

The tidal energy industry is progressing rapidly, but there are still barriers to overcome to realise the commercial potential of this sector. Large magnitude and highly variable loads caused by waves acting on the turbine are of particular concern. Composite blades with in-built bend-twist elastic response may reduce these peak loads, by passively feathering with increasing thrust. This could decrease capital costs by lowering the design loads, and improve robustness through the mitigation of pitch mechanisms. In this study, the previous research is extended to examine the performance of bend-twist blades in combined wave–current flow, which will frequently be encountered in the field. A scaled 3 bladed turbine was tested in the flume at IFREMER with bend-twist composite blades and equivalent rigid blades, sequentially under current and co-directional wave–current cases. In agreement with previous research, when the turbine was operating in current alone at higher tip speed ratios the bend-twist blades reduced the mean thrust and power compared to the rigid blades. Under the specific wave–current condition tested the average loads were similar on both blade sets. Nevertheless, the bend-twist blades substantially reduced the magnitudes of the average thrust and torque fluctuations per wave cycle, by up to 10% and 14% respectively.     

An experimental investigation into non-linear wave loading on horizontal axis tidal turbines

Tidal turbines are subject to large hydrodynamic loads from combinations of currents and waves, which contribute significantly to fatigue, extreme loading and power flow requirements. Physical model testing enables these loads and power fluctuations to be assessed and understood in a controlled and repeatable environment. In this work, a 1:15 scale tidal turbine model is utilised to further the fundamental understanding of the influence of waves on tidal turbines. A wide range of regular waves are generated in both following-current and opposing-current conditions. Wave frequencies range from 0.31 Hz to 0.55 Hz & wave heights from 0.025 m to 0.37 m in a fixed 0.81 m/s current velocity. Waves are selected and programmed specifically to facilitate frequency domain analysis, and techniques are employed to isolate the effect of non-linear waves on turbine power and thrust.Results demonstrate that wave action induces large variations in turbine power and thrust compared to current only conditions. For the range of conditions tested, peak values of thrust and power exceed current-only values by between 7%–65% and 13%–160% respectively. These wave-induced fluctuations are shown to increase with wave amplitude and decrease with wave frequency. Following wave conditions exhibit greater variations than opposing for waves with the same wave height and frequency due to the lower associated wavenumbers.A model is developed and presented to aid the understanding of the high-order harmonic response of the turbine to waves, which is further demonstrated using steady state coefficients under assumptions of pseudo-stationarity. This approach is proven to be effective at estimating wave-induced power and thrust fluctuations for the combinations of waves, currents and turbine state tested. The outcome of which shows promise as a rapid design tool that can evaluate the effect of site-specific wave–current conditions on turbine performance.