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1.
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
2.
Controlling effective interactions and spatial dispersion of nanoparticles in multiblock copolymer melts 下载免费PDF全文
Debapriya Banerjee Kenneth S. Schweizer 《Journal of Polymer Science.Polymer Physics》2015,53(16):1098-1111
The microscopic Polymer Reference Interaction Site Model theory is employed to study, for the first time, the effective interactions, spatial organization, and miscibility of dilute spherical nanoparticles in non‐microphase separating, chemically heterogeneous, compositionally symmetric AB multiblock copolymer melts of varying monomer sequence or architecture. The dependence of nanoparticle wettability on copolymer sequence and chemistry results in interparticle potentials‐of‐mean force that are qualitatively different from homopolymers. An important prediction is the ability to improve nanoparticle dispersion via judicious choice of block length and monomer adsorption‐strengths which control both local surface segregation and chain connectivity induced packing constraints and frustration. The degree of dispersion also depends strongly on nanoparticle diameter relative to the block contour length. Small particles in copolymers with longer block lengths experience a more homopolymer‐like environment which renders them relatively insensitive to copolymer chemical heterogeneity and hinders dispersion. Larger particles (sufficiently larger than the monomer diameter) in copolymers of relatively short block lengths provide better dispersion than either a homopolymer or random copolymer. The theory also predicts a novel widening of the miscibility window for large particles upon increasing the overall molecular weight of copolymers composed of relatively long blocks. The influence of a positive chi‐parameter in the pure copolymer melt is briefly studied. Quantitative application to fullerenes in specific copolymers of experimental interest is performed, and miscibility predictions are made. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1098–1111 相似文献
3.
在中国科学技术大学夏季学期的研究型实验课程"化学科研基础训练"中开设"壳聚糖的制备与表征"综合实验,以龙虾壳为原料,通过除蛋白、脱盐、脱色、脱乙酰等一系列反应,制备得到目标产物壳聚糖。运用红外光谱、核磁共振仪、黏度法、滴定等对产品的结构及性能进行表征。 相似文献
4.
5.
煤直接液化油中混合酚的分离研究 《燃料化学学报》2019,47(11):1298-1304
利用分子筛择形特点,对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物,采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变,分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响,以获得高性能固相吸附剂,并将其应用于180-190℃馏分段混合酚分离。结果表明,当分子筛硅铝比为25、粒径为3-5 μm时,分子筛的孔口结构调节效果最优;当正硅酸乙酯的最小用量为0.2 mL/g时,固相吸附剂的吸附量为0.03 g/g,对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化,导致对甲酚选择性的提高。进一步采用HZSM-5(1)吸附剂对真实煤直接液化油混合酚的分离中发现,苯酚和对甲酚的选择性均达到100%。 相似文献
6.
Mariam Hakami Dr. Geetanjali Deokar Jasmin Smajic Dr. Nitin M. Batra Prof. Pedro M. F. J. Costa 《化学:亚洲杂志》2021,16(11):1466-1474
In the last decade, catalytic chemical vapor deposition (CVD) has been intensively explored for the growth of single-layer graphene (SLG). Despite the scattering of guidelines and procedures, variables such as the surface texture/chemistry of catalyst metal foils, carbon feedstock, and growth process parameters have been well-scrutinized. Still, questions remain on how best to standardize the growth procedure. The possible correlation of procedures between different CVD setups is an example. Here, two thermal CVD reactors were explored to grow graphene on Cu foil. The design of these setups was entirely distinct, one being a “showerhead” cold-wall type, whereas the other represented the popular “tubular” hot-wall type. Upon standardizing the Cu foil surface, it was possible to develop a procedure for cm2-scale SLG growth that differed only by the carrier gas flow rate used in the two reactors. 相似文献
7.
在管式反应器中采用苯甲酸、聚乙二醇、固体古马隆树脂(S)、液体古马隆树脂(L)为添加剂来降低煤沥青中有害物质苯并芘的含量,以期使得煤沥青可绿色化应用。采用紫外-可见分光光度计分析煤沥青中苯并芘含量。考察了反应温度、反应时间、添加剂添加量、催化剂等工艺条件对添加剂脱除煤沥青中苯并芘的影响。结果表明,不同工艺条件能降低煤沥青中苯并芘的含量。在优化条件下,不同添加剂对苯并芘脱除率由高到低依次为:液体古马隆树脂、聚乙二醇、苯甲酸和固体古马隆树脂。分析其反应机理,这与催化剂的酸性相关,发生亲电取代反应。结果表明,液体古马隆树脂(L)在催化剂存在下对煤沥青中苯并芘脱除率可达73.0%,显示了良好的应用前景。 相似文献
8.
利用X射线光电子能谱(XPS)测试5,10,15,20-四-(对羟基苯基)卟啉单体和5,10,15,20-四-(对羟基苯基)卟啉自组装二聚体,并通过化学模拟得到卟啉自组装二聚体分子的最优构象.结果表明:两种卟啉化合物中氧原子的类型不同;在单体卟啉中未检测到瞬态表面光电压信号,卟啉自组装二聚体表现出较好的瞬态表面光伏特性;卟啉自组装二聚体的光限幅性质优于卟啉1单体. 相似文献
9.
Liming Fan Feng Wang Dongsheng Zhao Yuxin Peng Yuxin Deng Yinwei Luo Xiutang Zhang 《应用有机金属化学》2020,34(12):e5960
Guided by the self-penetrating features can improve the stability of metal organic frameworks (MOFs), an unprecedented 3D self-penetrated framework, {[Zn (tptc)0.5(bimb)]·H2O}n ( NUC-6 , here NUC corresponding to North University of China), with 3D (4,4)-c {86} net, was designed. Benefit from the high chemical stability and excellent luminescent property, NUC-6 can be act as an efficient multi-response chemo-sensor in detecting dichloronitroaniline pesticide and nitrofuran antibiotics in water with the detection limits are 116 ppb for DCN pesticide, 16 ppb for NFT antibiotic, and 12 ppb for NTZ antibiotic. Besides, the mechanisms of luminescence quenching were revealed from the viewpoint of internal filter effect (IFE) and photo-induced electron transfer (PET), implied by the optical spectroscopy and quantum chemical calculation. This work provides a promising strategy to design stable MOFs by improving the self-penetrating features and to expand their practical applications in the detection of organic pollutants in aqueous medium. 相似文献
10.
《Journal of separation science》2018,41(6):1319-1337
The present review discusses the theory and application of van't Hoff analysis in chiral chromatography, with main focus on liquid chromatography. The topics considered include the physical meaning of van't Hoff equation's parameters, interpretation of thermodynamic data in terms of retention and enantioseparation mechanisms, abnormal behavior of van't Hoff plots, and best practices to avoid biased results. 相似文献