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Dr. Waleed Alsalahi Dr. Adam W. Augustyniak Dr. Włodzimierz Tylus Prof. Dr. Anna M. Trzeciak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(6):e202103538
The new nanocomposites, Pd/C/ZrO2, PdO/ZrO2, and Pd/PdO/ZrO2, were prepared by thermal conversion of Pd@UiO-66-Zr−NH2 (MOF) in nitrogen or air atmosphere. The presence of Pd nanoparticles, uniformly distributed on the ZrO2 or C/ZrO2 matrix, was evidenced by transmission electron microscopy, scanning electron microscopy (SEM), Raman and X-ray Photoelectron Spectroscopy (XPS) methods. All pyrolysed composites retained the shape of the MOF template. They catalyze carbonylative Suzuki coupling under 1 atm CO with an efficiency significantly higher than the original Pd@UiO-66-Zr−NH2. The most active PdO/ZrO2 composite, formed benzophenone with TOF up to 1600 h−1, while by using Pd@UiO-66-Zr−NH2, much lower TOF values, 51–95 h−1, were achieved. After the reaction, PdO/ZrO2 was recovered with the same composition and catalytic activity. Very good results were also obtained in the transfer hydrogenation of benzophenones to alcohols with Pd/C/ZrO2 and PdO/ZrO2 catalysts under microwave irradiation. 相似文献
3.
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. 相似文献
4.
Laterally-coupled ridge-waveguide distributed feedback lasers fabricated without epitaxial regrowth steps have the advantages of process simplification and low cost. We present a laterally coupled grating with slots. The slots etched between the ridge and grating area are designed to suppress the lateral diffusion of carriers and to reduce the influence of the aspect-ratio-dependent-etching effect on the grating morphology in the etching process. Moreover, the grating height in this structure can be decreased to lower the aspect ratio significantly, which is advantageous over the conventional laterally coupled ridge waveguide gratings. The effects of five main structural parameters on the coupling characteristics of gratings are studied by MODE Solutions. It is found that varying the lateral width of the grating can be used as an effective way to tune the coupling strength; narrow slots (100 nm and 300 nm) and wide ridge (2 μm-4 μm) promote the stability of grating coupling coefficient and device performance. It is important to note that the grating bottom should be fabricated precisely. The comparative study of carrier distribution and mode field distribution shows that the introduction of narrow slots can strengthen the competitive advantage and stability of the fundamental mode. 相似文献
5.
The N–N bond is present in many important organic compounds, such as hydrazines, pyrazoles, azos, etc. Many methods based on transition metal catalyzed N–N coupling or functionalization of hydrazine have been reported for the synthesis of N–N containing organic compounds. In recent years, electrochemical dehydrogenative N–H/N–H coupling has become a powerful tool for the construction of N–N bearing organic compounds. The electrochemical methods employ electrons as traceless redox reagents instead of chemicals and produce hydrogen as the only byproduct. In this review, we summarize the recent advances in the electrochemical dehydrogenative N–H/N–H coupling reactions with focus on the mechanistic insights and synthetic applications of these transformations. 相似文献
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Georgios Velkos Denis S. Krylov Kyle Kirkpatrick Lukas Spree Vasilii Dubrovin Bernd Büchner Stanislav M. Avdoshenko Valeriy Bezmelnitsyn Sean Davis Paul Faust James Duchamp Harry C. Dorn Alexey A. Popov 《Angewandte Chemie (International ed. in English)》2019,58(18):5891-5896
The azafullerene Tb2@C79N is found to be a single‐molecule magnet with a high 100‐s blocking temperature of magnetization of 24 K and large coercivity. Tb magnetic moments with an easy‐axis single‐ion magnetic anisotropy are strongly coupled by the unpaired spin of the single‐electron Tb?Tb bond. Relaxation of magnetization in Tb2@C79N below 15 K proceeds via quantum tunneling of magnetization with the characteristic time τQTM=16 462±1230 s. At higher temperature, relaxation follows the Orbach mechanism with a barrier of 757±4 K, corresponding to the excited states, in which one of the Tb spins is flipped. 相似文献
8.
Julia Holz Camilla Pfeffer Hualiang Zuo Dennis Beierlein Gunther Richter Elias Klemm Ren Peters 《Angewandte Chemie (International ed. in English)》2019,58(30):10330-10334
Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C ?C cross‐coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C ?C bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent. 相似文献
9.
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. 相似文献
10.
固体氧化物燃料电池的翘曲会影响电极-盖板界面的接触情况,从而影响电化学性能,对相关制造工艺提出了很大的挑战.为了分析燃料电池平面度对放电过程的影响,揭示其潜在的风险,我们建立了两个基于有限元法的仿真模型,对考虑平面度缺陷的燃料电池封装和放电进行分析.在对固体氧化物燃料电池进行平面度测量的基础上,首先建立了具有真实燃料电池翘曲特性的几何模型,分析封装过程中接触压力的分布情况.然后将接触电阻的仿真结果导入到三维多物理场耦合模型中,模拟具有平面度缺陷的燃料电池电化学性能.计算结果展示了燃料电池两侧封装过程中接触压力的分布情况.通过对比有接触电阻和无接触电阻的燃料电池电流密度,分析了电池与盖板的接触对放电过程的影响.结果表明,燃料电池的凹陷面较难达到满意的接触状态,需要比凸起面更大的封装压力.燃料电池表面接触电阻的变化将引起电流传导路径的变化,产生局部高电流或低电流.这项工作强调了在燃料电池中保持均匀分布的接触电阻的重要性,为今后的优化工作奠定了基础. 相似文献