Continuous Synthesis of Aryl Amines from Phenols Utilizing Integrated Packed‐Bed Flow Systems

Aryl amines are important pharmaceutical intermediates among other numerous applications. Herein, an environmentally benign route and novel approach to aryl amine synthesis using dehydrative amination of phenols with amines and styrene under continuous‐flow conditions was developed. Inexpensive and readily available phenols were efficiently converted into the corresponding aryl amines, with small amounts of easily removable co‐products (i.e., H₂O and alkanes), in multistep continuous‐flow reactors in the presence of heterogeneous Pd catalysts. The high product selectivity and functional‐group tolerance of this method allowed aryl amines with diverse functional groups to be selectively obtained in high yields over a continuous operation time of one week.     

共价有机框架材料在固定化酶及模拟酶领域的应用

共价有机框架(Covalent Organic Frameworks, COFs)是一类由轻质元素通过可逆共价键连接而成的晶型多孔有机材料。因具有高比表面积、低密度、规则的孔隙和易于功能化等独特的性能和结构,COFs在气体吸附、化学传感和非均相催化等领域有着广泛的应用前景。近年来,COFs逐渐显现出在固定化酶和模拟酶领域的应用潜力,由于可以轻松定制COF上的官能团以保持COF与酶之间的特定相互作用,因此COF成为有吸引力的酶固定基质。此外,COF的连续且封闭的开放通道为渗透酶提供了良好的微环境。同时,探索了COF模拟酶的特征,通过“从下到上”的方法或后修饰策略设计了COF模拟酶。这不仅扩展了固定化酶载体材料的研究和应用范围,还为模拟酶仿生催化提供了新的研究思路。本文综述了COFs固定化酶和作为纳米材料模拟酶(纳米酶)在生物催化领域的研究进展,详细讨论了COFs载体的合成和功能化策略、固定化酶方式,以及COFs纳米酶的设计理念、催化活性和选择性等内容。最后总结了目前COFs在酶催化领域所面临的挑战和未来发展的机遇。     

共价有机框架材料催化研究进展

共价有机框架材料(COFs)是一类具有高比表面积、高孔隙率、高结晶度的结构多样性多孔材料.由于COFs具有可设计性、易功能化的特点,可通过"自上而下"或者后修饰策略将具有催化活性的官能团或金属颗粒嵌入到材料骨架当中,从而设计出高效催化剂. COFs已逐渐在多相催化及其它催化领域展现出非常大的应用价值.本文综述了COFs作为催化剂载体在多种催化反应中的合成策略与应用,对COFs催化剂的现状进行了总结与展望,同时指出该领域面临的问题与挑战.     

基于尺度视角下的“催化剂”拓展课教学*

通过对Fe3+催化过氧化氢分解的实验过程的探究,证实了有的均相催化剂参与反应后化学性质是有改变的,完善了对催化剂概念的认识。进一步基于尺度视角设计并制备了新型的非均相催化剂磁性Fe3O4纳米粒子,并对其催化双氧水分解的过程进行了实验探究,对其是否损耗与Fe3+的催化过程形成对比,对均相催化剂和非均相催化剂进行了比较与评价。以尺度为思考问题的出发点,引导学生理解科研前沿(单原子催化剂)的设计思想,构建学生认识物质的尺度观念,促进学生进一步认识科学本质和学科价值,培养学生的创新意识。     

功能化氮化碳对Pd基甲酸分解制氢催化剂性能的促进作用

负载型Pd基催化剂是最有效的甲酸分解(FAD)制氢催化剂之一,其中氮化碳载体的N含量较高,但是通常一步热解法制备的氮化碳为块状,难以有效分散表面金属纳米粒子(NPs)。 本文通过将尿素前驱体在溶剂化作用后热解得到功能化氮化碳,以此为载体,利用阴离子交换和硼氢化钠直接还原法制备了功能化氮化碳负载的Pd基催化剂(Pd/C₃N₄-F)。 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)对材料结构进行表征,并通过气体质量流量计测试了催化剂的性能。 Pd/C₃N₄-F具有优异的催化FAD制氢性能,30 ℃下的初始TOF(总转换频率)值和质量比活性分别为1824 h^-1和17.14 mol_H2/(g_Pd·h)。 对产物的气相色谱分析结果也表明没有副产物CO生成,表明催化剂具有优异的选择性。 并且随着温度的升高(30～40 ℃),催化剂性能逐渐提高。     

光电化学催化中的富勒烯基材料：机理及应用

光催化和电化学催化在现代清洁能源转化中发挥了无可替代的作用。[60]富勒烯(C_(60))材料因其独特的结构与性能而被广泛用于各类光电催化剂的开发中,并取得了令人瞩目的成果。我们简介了C_(60)的基本性质以及富勒烯基(包括C_(60)笼外衍生物和衍生碳材料)光电催化剂的制备方法,综述了C_(60)及其衍生材料在光催化和电化学催化领域中的研究进展,就其在光电化学催化应用中所起到的主要作用、工作机理以及优化策略进行了讨论。并对C_(60)基催化剂发展中的主要问题与挑战进行了总结和展望。     

Influence of lanthanum on the performance of Zr-Co/activated carbon catalysts in Fischer-Tropsch synthesis

The influence of La loading on Zr-Co/activated carbon （AC） catalysts has been studied for Fischer-Tropsch synthesis. The catalyst samples were characterized by XRD, TPR, CO-TPD, and temperature programmed CO hydrogenation. The catalytic property was evaluated in a fixed bed reactor. The experimental results showed that CO conversion increased from 86.4% to 92.3% and the selectivity to methane decreased from 14.2% to 11.5% and C5＋ selectivity increased from 71.0% to 74.7% when low La loading （La = 0.2wt%） was added into the Zr-Co/AC catalyst. However, high loadings of La （La = 0.3-1.0 wt%） would decrease catalyst activity as well as the C5＋ selectivity and increase methane selectivity. XRD results displayed that La-modified Zr-Co/AC catalyst had little effect on the dispersion of Co catalyst. But, the results of TPR, CO-TPD, and temperature programmed CO hydrogenation techniques indicated that the extent of cobalt reduction was found to greatly influence the activity and selectivity of the catalyst. The addition of a small amount of La increased the reducibility of the Zr-Co/AC catalyst and restrained the formation of methane and improved the selectivity to long chain hydrocarbons. However, excess of La led to the decrease of the reducibility of Co catalyst thus resulted in higher methanation activity.     

Synthesis and microstructure investigation of heterogeneous metal-plasma polymer Ag/HMDSO nanoparticles

Metal-polymer nanocomposites have gained increasing attention due to the wide potential applications field. Synthesis of nanoparticles from the gas phase is an intensively studied alternative to the chemical preparation methods. We present a one-step procedure that combines magnetron-based gas aggregation cluster source of silver nanoparticles and simultaneous plasma-enhanced chemical vapour deposition of hexamethyldisiloxane (HMDSO). The key parameter of the process, significantly influencing the morphology and microstructure of studied nanoparticles, was found to be the amount of HMDSO added to the deposition chamber as witnessed by small angle X-ray scattering and X-ray diffraction methods combined with transmission electron microscopy and UV–Vis spectrophotometry. The presence of HMDSO in the chamber leads to changes in the size distribution and also in the architecture of prepared nanoparticles. The increasing amount of HMDSO induces the formation of individual core-shell nanoparticles, chains of core-shell nanoparticles, and for the highest concentration of HMDSO, the synthesis of multi-core-shell nanoparticles. The size of crystallites in the silver cores of nanoparticles decreases with addition of HMDSO, which prevents further aggregation.     

CoFe2O4@SiO2-NH2-CoII NPs catalyzed Hantzsch reaction as an efficient,reusable catalyst for the facile,green, one-pot synthesis of novel functionalized 1,4-dihydropyridine derivatives

A magnetically heterogeneous CoFe₂O₄@SiO₂-NH₂-Co^II nanoparticle was synthesized by the immobilization of Co (II) complex onto CoFe₂O₄@SiO₂ nanoparticles, and the heterogeneous magnetic nanocatalyst was characterized by XRD, TEM, TGA, EDX, and FT-IR techniques. Then, the green and reusable method was introduced for a multicomponent synthesis of 1,4-dihydropyridine derivatives via Hantszch reaction. The synthesis of 1,4-dihydropyridine derivatives was proceeded by the reaction of aldehyde, ethyl acetoacetate, and ammonium acetate in the presence of this magnetic nanocatalyst in EtOH/Water (1:1). Simple work-up, short reaction times, excellent yields (60–96%) as well as green solvent are some advantages of this novel approach, and the corresponding products were purified with no need for chromatographic separation.     

Selective and solventless oxidation of organic sulfides and alcohols using new supported molybdenum (VI) complex in microwave and conventional methods

A new dioxo-molybdenum (VI) complex supported on functionalized Merrifield resin ( MR-Mo ) has been synthesized and characterized by elemental, scanning electron mcroscopy, energy-dispersive X-ray analysis, TGA, Brunauer–Emmett–Teller method, powder-X-ray diffraction, Fourier transform infrared, X-ray photoelectron spectroscopy and DRS–UV–vis analysis. The virgin Merrifield resin ( MR ) was functionalized by carbonylation followed by Schiff base formation with ethanolamine ( MR-SB ). Experimental data showed that the Schiff base coordinated with the MoO₂²⁺ moiety via O- and N-atoms. The catalytic activity of MR-Mo was explored under solventless conditions toward the oxidation of organic sulfides and alcohols using 30% aqueous H₂O₂ as oxidant. The oxidation reactions were conducted under microwave and conventional methods. The microwave-assisted oxidation reactions were found to be many times faster than the conventional methods. The oxidation reactions were selective and formed sulfoxides or aldehydes as the sole product with superior TOF values among the molybdenum (VI)-based complexes. Besides these, the MR-Mo was purely heterogeneous in nature and can be recycled for at least five reaction cycles without the loss of catalytic efficiency and product selectivity.