The efficient synthesis of 3-hydroxyoxetane-3-carboxamides by the reaction of carbamoylsilanes with oxetan-3-one

1. Download : Download high-res image (67KB)
2. Download : Download full-size image

     

Study of Manganese Promoter on a Precipitated Iron-Based Catalyst for Fischer-Tropsch Synthesis

The effects of Manganese(Mn)incorporation on a precipitated iron-based Fischer-Tropsch synthesis(FTS)catalyst were investigated using N_2 physical adsorption,air differential thermal analysis (DTA),H_2 temperature-programmed reduction(TPR),and M(?)ssbauer spectroscopy.The FTS perfor- mances of the catalysts were tested in a slurry phase reactor.The characterization results indicated that Mn increased the surface area of the catalyst,and improved the dispersion ofα-Fe_2O_3 and reduced its crystallite size as a result of the high dispersion effect of Mn and the Fe-Mn interaction.The Fe-Mn inter- action also suppressed the reduction ofα-Fe_2O_3 to Fe_3O_4,stabilized the FeO phase,and(or)decreased the carburization degree of the catalysts in the H_2 and syngas reduction processes.In addition,incorporated Mn decreased the initial catalyst activity,but improved the catalyst stability because Mn restrained the reoxidation of iron carbides to Fe_3O_4,and improved further carburization of the catalysts.Manganese suppressed the formation of CH_4 and increased the selectivity to light olefins(C_(2-4)~=),but it had little effect on the selectivities to heavy(C_(5 )) hydrocarbons.All these results indicated that the strong Fe-Mn interaction suppressed the chemisorptive effect of the Mn as an electronic promoter,to some extent,in the precipitated iron-manganese catalyst system.     

探究Cu/ZnO相互作用对CO2加氢制甲醇反应性能的影响

Using renewable green hydrogen and carbon dioxide (CO₂) to produce methanol is one of the fundamental ways to reduce CO₂ emissions in the future, and research and development related to catalysts for efficient and stable methanol synthesis is one of the key factors in determining the entire synthesis process. Metal nanoparticles stabilized on a support are frequently employed to catalyze the methanol synthesis reaction. Metal-support interactions (MSIs) in these supported catalysts can play a significant role in catalysis. Tuning the MSI is an effective strategy to modulate the activity, selectivity, and stability of heterogeneous catalysts. Numerous studies have been conducted on this topic; however, a systematic understanding of the role of various strengths of MSI is lacking. Herein, three Cu/ZnO-SiO₂ catalysts with different strengths of MSI, namely, normal precipitation Cu/ZnO-SiO₂ (Nor-CZS), co-precipitation Cu/ZnO-SiO₂ (Co-CZS), and reverse precipitation Cu/ZnO-SiO₂ (Re-CZS), were successfully prepared to determine the role of such interactions in the hydrogenation of CO₂ to methanol. The results of temperature-programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) characterization illustrated that the MSI of the catalysts was considerably affected by the precipitation sequence. Fourier transform infrared reflection spectroscopy (FT-IR) results indicated that the Cu species existed as CuO in all cases and that copper phyllosilicate was absent (except for strong Cu-SiO₂ interaction). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂O chemical titration results revealed that strong interactions between the Cu and Zn species would promote the dispersion of Cu species, thereby leading to a higher CO₂ conversion rate and improved catalytic stability. As expected, the Re-CZS catalyst exhibited the highest activity with 12.4% CO₂ conversion, followed by the Co-CZS catalyst (12.1%), and the Nor-CZS catalyst (9.8%). After the same reaction time, the normalized CO₂ conversion of the three catalysts decreased in the following order: Re-CZS (75%) > Co-CZS (70%) > Nor-CZS (65%). Notably, the methanol selectivity of the Re-CZS catalyst was found to level off after a prolonged period, in contrast to that of Co-CZS and Nor-CZS. Investigation of the structural evolution of the catalyst with time on stream revealed that the high methanol selectivity of the catalyst was caused by the reconstruction of the catalyst, which was induced by the strong MSI between the Cu and Zn species, and the migration of ZnO onto Cu species, which caused an enlargement of the Cu/ZnO interface. This work offers an alternative strategy for the rational and optimized design of efficient catalysts.     

错配核酸的研究进展

本文通过介绍多种错配核酸的结构及其热力学性质，详细地描述了非Watson-Crick配对核酸的最新进展。这方面的研究有利于阐明生物体内错配核酸的识别修复机理及核酸二级结构的预测，并为合理设计新的人工核酸修复酶提供了理论基础。     

环丙基甲基酮的合成研究进展

环丙基甲基酮是合成环丙氟哌酸类广谱抗菌药物和抗艾滋特效药依法韦仑的重要中间体,在医药、化工及农林等领域均有广泛应用。环丙基甲基酮的合成方法大致分为4类,分别以酮类、酯类、醇类及呋喃有机物为原料,在一定条件下生成环丙基甲基酮粗品,经萃取及精馏得到环丙基甲基酮纯品。本文综述了环丙基甲基酮的合成研究进展。     

(XN)4R4簇合物的结构与化学键

用密度泛函理论,在B3LYP/6-311G水平上,对(XN)4R4 (X=C,Si,Ge;R=H,CH3,NH2,OH)及合成的先驱化合物(XN)2R2进行几何构型、电子结构、振动频率和化学反应焓变等进行了研究.结果表明,(RCN)4比(CNR)4更稳定.所有簇合物的零点能EZP值,R=H时最小,R=CH3时最大,R配位原子依次为C、N和O时,EZP值逐渐减小.     

Spectrophotometric determination of lead in vegetables with dibromo-p-methyl-carboxysulfonazo

A new highly sensitive and selective chromogenic reagent dibromo-p-methyl-carboxysulfonazo (DBMCSA) was synthesized and studied for the spectrophotometric determination of lead in detail. In 0.25 M phosphoric acid medium, which greatly increases the selectivity, lead reacts with DBMCSA to form a 1:2 blue complex, having a sensitive absorption peak at 648 nm. Under the optimal conditions, Beer's law is obeyed over the range from 0 to 0.8 μg ml⁻¹ Pb(II) and the apparent molar absorptivity is 1.04×10⁵ l mol⁻¹ cm⁻¹. The detection limit and the variation coefficient were found to be 2.14 ng ml⁻¹ and 1.0%, respectively. It is found that, except for Ca(II) and Ba(II), all foreign ions studied do not interfere with determination. The interference caused by Ca(II) and Ba(II) can be easily eliminated by prior extraction with potassium iodide-methylisobutylketone. The method has been applied to the determination of lead in vegetables with satisfactory results.     

Catalytic Oxidation of Dimethyl Ether to Dimethoxymethane over Cs Modified HaPW12O40/SiO2 Catalysts

The attractive utilization route for one-step catalytic oxidation of dimethyl ether to dimethoxymethane was successfully carried out over the H3PW12O40（40%）/SiO2 catalyst, modified by Cs, K, Ni, and V. The Cs modification of H3PW12O40（40%）/SiO2 gave the most promising result of 20% dimethyl ether conversion and 34.8% dimethoxymethane selectivity. Dimethoxymethane could be synthe- sized via methoxy groups decomposed from dimethyl ether through the synergistic effect between the acid sites and the redox sites of Cs modified H3PW12O40（40%）/SiO2.     

Migration of 99Tc in a Weak Loess Aquifer: A Field Column Experiment

The migration of ⁹⁹Tc in a weak loess aquifer was investigated in-situ with undisturbed aquifer medium columns. The columns were obtained horizontally at a depth of 3236 m in an Underground Research Facility (URF). Quartz containing ³H (HTO) and ⁹⁹Tc (in the form of ⁹⁹TcO₄ ^-) was introduced into one end of the columns and the columns were covered tightly. Aquifer water was introduced into the columns directly from an experimental shaft in the UFR. Effluents from the columns were collected and the activity of ³H and ⁹⁹Tc were determined with a liquid scintillation analyzer. The breakthrough curves of ³H and ⁹⁹Tc indicate that ⁹⁹Tc migrates a little faster than that ³H does in the aquifer.     

2-巯基苯并咪唑保护的铜纳米团簇的制备及银离子检测

以2-巯基苯并咪唑为保护剂,聚乙烯吡咯烷酮为稳定剂,水合肼为还原剂,“一锅法”合成2-巯基苯并咪唑保护的,高稳定性、强荧光、大斯托克斯位移的铜纳米团簇(Cu NCs),并用于检测水样中的银离子含量。采用透射电子显微镜(TEM)和X射线光电子能谱(XPS)对铜纳米团簇的结构进行表征,通过荧光光谱和紫外可见光谱对其光学性能进行研究。研究表明:该铜纳米团簇的最大激发和发射波长分别为340和558 nm,在日光灯和紫外灯下分别为无色和橙色。Cu NCs具有较高的分散性,尺寸大小为2~3 nm。在最佳反应条件下,铜纳米团簇可以选择性地被银离子猝灭,且灵敏度高,线性范围为1~40μmol/L,检测限为0.5μmol/L。该方法用于检测实际水样(自来水、湖水)中银离子的浓度,结果令人满意,表明在环境监测中有非常高的应用价值。