氮杂冠醚合成中的双功能基试剂

综述了氮杂冠醚合成中的双功能基试剂的进展。着重讨论了典型的双功能基试剂,如取代多甘醇、二胺、氨基二醇、二卤代物、二醛和二酮以及3-烷氧丙烯醛等的制备方法。     

Synthesis of p‐aminophenol from the hydrogenation of nitrobenzene over metal–solid acid bifunctional catalyst

BACKGROUND: A single‐step conversion of nitrobenzene (NB) to p‐aminophenol (PAP) through catalytic hydrogenation is a widely used synthesis route for PAP. The main shortcoming of this route is the use of sulfuric acid for rearrangement of the phenylhydroxylamine (PHA) intermediate. In this paper, S₂O₈^2?/ZrO₂ (PSZ) solid acid and Pt‐S₂O₈^2?/ZrO₂ (Pt‐PSZ) bifunctional catalysts were prepared for the synthesis of PAP in non‐acid medium. RESULTS: Calcination temperature has a substantial effect on the acidity, structure and activity for PHA rearrangement of PSZ. The highest PAP yield was 33.8% over PSZ calcined at 823 K when the reaction was carried out in water at 423 K. A high PAP yield of 23.9% was achieved by a single‐step reaction of nitrobenzene over Pt‐PSZ bifunctional catalysts. CONCLUSION: PSZ solid acid exhibits high activity for PHA rearrangement. Perfect tetragonal ZrO₂ and much stronger acid sites play important roles in catalytic activity. Inhibiting the hydrogenation activity by reducing the amount of Pt loading on Pt‐PSZ can improve the competition of PHA rearrangement on acid sites with hydrogenation of PHA on metal active sites, resulting in better selectivity to PAP. Copyright © 2008 Society of Chemical Industry     

Intercalated clays from pentaerythritol stearate for use in polymer nanocomposites

Smectite clays treated with quaternary ammonium salts have been utilized for decades in paints, greases, cosmetics, and personal care products as rheological modifiers. They have also been used in industrial wastewater treatment extensively. In more recent times these surface modified clays have demonstrated benefits in polymer/clay nanocomposites. The use of quaternary ammonium modifiers limits the usefulness of these composites in food packaging because they are not approved for direct food contact. It would be advantageous to have surface modifying chemicals acceptable for direct food contact in these composites. This article reports research conducted on a promising surface modifier pentaerythritol stearate (PS), which is approved by the FDA for inclusion in food as a preservative. The surface modification of montmorillonite with PS is reported in detail as well as the production of nanocomposites with selected polymers made with the modified clay. Molecular modeling and purification of commercial PS samples indicate that the mono‐ and diesters are the critical surface modifiers, although the as received commercial material works well in forming intercalated clay complexes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

H2-O2气氛中丙烯环氧化反应研究进展

对H2-O2气氛中丙烯环氧化反应所采用的催化剂、反应器及操作方式进行了评述.综合分析了所使用的钯(金或银)/钛硅分子筛(或氧化钛)双功能催化剂的各项性能指标以及所采用的反应器型式.结合H2-O2直接合成H2O2所用催化剂,对原位氧化丙烯反应过程进行了系统描述.指出进一步的研究方向是借助反应或分离耦合技术,创造有利于原位生成的H2O2及时进行环氧化而避免分解的操作环境,包括催化剂表面状态、反应器型式、溶剂体系和操作方式,并提出以丙烷路线经脱氢、环氧化是制取环氧丙烷的最佳组合.     

Syndiotactic Polystyrene/Organoclay Nanocomposites: Synthesis via In Situ Coordination‐Insertion Polymerization and Preliminary Characterization

Summary: Syndiotactic polystyrene (sPS)/organophilic clay nanocomposites were obtained by in situ coordination‐insertion polymerization of styrene. Two cationic surfactants (alkylammonium and alkylphosphonium) were used for the intercalation of montmorillonite (MMT). For each organically modified clay, three protocols were performed using an MAO‐activated hemi‐metallocene catalyst, in order to compare the influence of experimental conditions on the composite microstructure and on its thermal stability. The microstructures of nanocomposites were investigated by wide angle X‐ray scattering and DSC. Partially exfoliated or intercalated materials were obtained in all cases and a decrease of crystallinity is observed. Thermal properties were also studied by DSC and thermogravimetric analysis. The presence of clay does not have a strong influence on the sPS thermal transitions but the thermal decomposition process of the material was slowed down in the presence of few organoclay percents, particularly in the degradation beginning. The influence of these two organically modified clays on the thermal stability of the material is discussed.

Gel and suspension formed from the combination of cloisite with toluene (left) and styrene (right), respectively.     

双活性基活性染料真丝绸染色工艺研究

双活性基活性染料用于真丝绸染色有诸多影响因素：缚酸剂用碳酸氢钠比碳酸钠的固色率高用量在2％～4％，pH为8～9时最为合适：染色温度从60℃升到85℃时固色率提高3％～8％，超过85℃时易造成“灰伤”．当元明粉的用量从30g／l升到60g／l时上染率和固色率提高10％。随着浴比的增加，其固色率会有不同程度的降低，在实验条件下，浴比为1：40最好。通过上染曲线，讨论了染色过程的控制。     

低CO2选择性的合成气制轻烯烃双功能催化剂

为开发高活性、高收率的合成气制低碳烯烃（STO）双功能催化剂，通过共沉淀法制备非化学计量尖晶石Zn-Cr-Al氧化物，对其织构性质、晶体结构、形貌特征以及表面电荷性质等进行研究。结果表明添加过量锌能够促进晶体粒径减小，表面氧空位增多。其中Zn/(Cr+Al)摩尔比为1.25时锌含量较为适宜，将其与SAPO-34沸石分子筛结合为双功能催化剂用于STO性能研究。在进气n(H2):n(CO)=2:1，3000 mL/(gcat·h)，3.2 MPa，400 ℃反应条件下，实现46.9% CO转化率，C2-4烯烃收率高达15.9%，高于大部分已有文献报道（8~14%），特别是副产物CO2选择性仅29.2%，低于普遍报道的40~50% CO2选择性。并且催化剂运行100 h后活性良好，稳定的催化性能使其具有工业应用价值。     

Roles of interaction between components in CZZA/HZSM-5 catalyst for dimethyl ether synthesis via CO2 hydrogenation

The roles of interaction between two catalyst components in CuO–ZnO–ZrO₂–Al₂O₃ (CZZA)/HZSM-5 bifunctional catalyst for dimethyl ether (DME) synthesis via carbon dioxide hydrogenation were investigated. It was found that CZZA catalyst showed excellent stability during methanol (MeOH) synthesis for 100 h, while there was a severe loss of catalytic activity in the bifunctional catalyst for DME synthesis. Hence, the effects of different degrees of intimacy of two catalyst components were studied for DME synthesis, including mixed and separated modes. For the mixed mode, the particle size of catalysts and the amount of reaction intermediates were proven to influence the catalyst deactivation. For the separated mode, the catalysts showed rapid deactivation within a short time. Various characterizations indicated that the remarkable deactivation of separated mode was mainly caused by the decrease of copper active centers (e.g., sintering and oxidation) and blockage of acid sites via increased coke deposition on HZSM-5.     

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 文章分析了连铸坯表面纵向裂纹的成因，并提出与化学成份和保护渣质量有很大关系。     

The Heterointerface between Fe1/NC and Selenides Boosts Reversible Oxygen Electrocatalysis

The rational design and construction of efficient and inexpensive bifunctional oxygen electrocatalysts are highly desirable for the development of rechargeable Zn–air batteries (ZABs). Although single-atom Fe sites anchored on N-doped carbon catalysts (Fe₁/NC) ensure high oxygen reduction reaction activity, their unitary atomically dispersed active center faces difficult condition in catalyzing oxygen evolution reaction simultaneously. Herein, a composite catalyst containing heterointerface between Fe₁/NC and selenides ((Fe,Co)Se₂) is constructed. The obtained (Fe,Co)Se₂@Fe₁/NC exhibits extremely narrow potential gap of 0.616 V and remarkable stability in alkaline media, outperforming the benchmark catalysts (Pt/C+RuO₂: 0.720 V). Experimental results and density functional theory calculations reveal that heterointerface between Fe₁/NC and (Fe,Co)Se₂ accelerates the electron transfer and provides more moderate adsorption sites, which endow (Fe,Co)Se₂@Fe₁/NC with extremely high bifunctional oxygen catalytic activity. This study not only provides a superior bifunctional catalyst for ZABs, but also enriches the application of single-atom catalysts in multifunctional energy storage and conversion devices.