From Colloidal Dispersions of Zeolite Monolayers to Effective Solid Catalysts in Transformations of Bulky Organic Molecules: Role of Freeze-Drying and Dialysis

We investigated the properties and catalytic activity of zeolites with MWW topology obtained by unprecedented liquid exfoliation of the MCM-56 zeolite into solutions of monolayers and isolation/reassembly of the dispersed layers by various methods, with optional purification by dialysis or ammonium exchange. The layers were recovered by flocculation with alcohol or ammonium nitrate and freeze-drying. Flocculation alone, even with ammonium nitrate, did not ensure removal of residual sodium cations resulting in catalysts with low activity. Dialysis of the solutions with dispersed monolayers proved to be efficient in removing sodium cations and preserving microporosity. The monolayers were also isolated as solids by freeze-drying. The highest BET area and pore volume obtained with the freeze-dried sample confirmed lyophilization efficiency in preserving layer structure. The applied test reaction, Friedel–Crafts alkylation of mesitylene, showed high benzyl alcohol conversion due to increased concentration of accessible acid centers caused by the presence of secondary mesoporosity. The applied treatments did not change the acid strength of the external acid sites, which are the most important ones for converting bulky organic molecules. Zeolite acidity was not degraded in the course of exfoliation into monolayers, showing the potential of such colloid dispersions for the formation of active catalysts.     

C4/C5烃催化裂解制低碳烯烃的研究进展

从催化剂类型、裂解工艺、催化裂解的影响因素和裂解机理4个方面对国内外C4／C5烃催化裂解制低碳烯烃的研究进行了综述。催化裂解制低碳烯烃催化剂主要采用ZSM-5分子筛系列催化剂，在此基础上发展了酸改性或水热改性高硅ZSM系列分子筛及介孔MCM41分子筛。总结了国内外C4／C5烃的裂解工艺，认为影响催化裂解的主要因素是裂解原料、催化剂类型及工艺条件。目前，裂解机理主要是自由基与碳正离子机理相结合的机理。并简述了本课题组目前有关C4烷烃催化裂解的主要研究进展。     

C4/C5烃催化裂解制低碳烯烃的研究进展

从催化剂类型、裂解工艺、催化裂解的影响因素和裂解机理4个方面对国内外C4/C5烃催化裂解制低碳烯烃的研究进行了综述。催化裂解制低碳烯烃催化剂主要采用ZSM-5分子筛系列催化剂,在此基础上发展了酸改性或水热改性高硅ZSM系列分子筛及介孔MCM-41分子筛。总结了国内外C4/C5烃的裂解工艺,认为影响催化裂解的主要因素是裂解原料、催化剂类型及工艺条件。目前,裂解机理主要是自由基与碳正离子机理相结合的机理。并简述了本课题组目前有关C4烷烃催化裂解的主要研究进展。     

无模板剂预晶化液添加法合成ZSM-5分子筛

研究了旋转烘箱中无模板剂条件下,预晶化液添加对合成ZSM-5分子筛的影响。系统研究了预晶化液加入量对合成分子筛晶化速率及颗粒大小的影响。采用X射线衍射,扫描电镜,N2吸附-脱附,和激光粒度分布等分析方法对合成的ZSM-5分子筛样品的物化性能进行了表征。结果表明,预晶化液的添加可以明显加快分子筛的晶化速率,预晶化液添加量为33.3wt%时达到最大结晶度的合成时间由未添加时的48 h减少到24 h。添加预晶化液的母液在150℃晶化24 h时所得ZSM-5分子筛团聚体的颗粒大小随着预晶化液加入量的增大而增大,由5.5μm增大到26.3μm。团聚体颗粒的比表面积比未添加预晶化液得到的分子筛(292 m2.g-1)有了不同程度的提高,如添加量为33.3wt%时为394 m2.g-1。对预晶化液添加法合成ZSM-5分子筛团聚体颗粒的生长机理进行了讨论。     

The Role of Order in the Amplification of Light‐Energy Conversion in a Dye‐Sensitized Solar Cell Coupled to a Photonic Crystal

We investigate the cause of amplification of light‐energy conversion when coupling a nc‐TiO₂ film to a TiO₂ inverse opal by comparing it to an inverse TiO₂ glass (i‐TiO₂‐g) fabricated with the exact monodisperse air–hole size as an inverse opal with a stop band at 600 nm (600‐i‐TiO₂‐o). A significant twofold average gain in the photon‐to‐current conversion efficiency is measured to the red of the stop band at the 600‐i‐TiO₂‐o/nc‐TiO₂ bilayer under front‐wall and back‐wall illumination, greater than the gain within the stop band. A smaller amplification is measured under front‐wall illumination—and no gain is measured under back‐wall illumination—for i‐TiO₂‐g/nc‐TiO₂ at these energies. The photonic crystal therefore causes trapping of light through the bilayer, not only within the gap but also to the red, at frequencies within its dielectric band. This light‐trapping effect is found to be dependent on structural order, as a highly disordered inverse glass film with the same air–hole size and thickness does not yield the same gain. A drop in the transmission of light is measured within the same frequencies to the red of the stop band upon adding nc‐TiO₂ to 600‐i‐TiO₂‐o, consistent with light trapping in the bilayer.     

晶粒大小对ZSM-5分子筛甲醇制低碳烯烃催化性能的影响

对三种HZSM-5分子筛进行Ca改性,获得两组酸性接近的催化剂,考察了晶粒大小对甲醇制低碳烯烃(MTO)反应的影响。通过进一步与Na改性的比较,探讨了Ca在催化反应中的作用。采用扫描电镜(SEM)测定晶粒大小及形貌,氨气程序升温脱附(NH3-TPD)及吡啶红外吸附(Py-IR)表征催化剂的酸性。MTO催化性能测定结果表明,HZSM-5的低碳烯烃选择性较低且下降较快,催化活性降低也快;Ca改性降低酸性,提高了低碳烯烃选择性和催化稳定性;晶粒大小主要影响催化稳定性,小晶粒分子筛催化剂稳定性更好。高Ca含量改性效果更好;钠改性也提高了低碳烯烃选择性,但其稳定性较差。对于HZSM-5和Ca/HZSM-5,小晶粒的催化剂具有较好的催化稳定性。提出Ca参与了催化反应,MTO是一个酸碱协同作用的催化过程。     

Asymmetric Amplification in the Catalysis with Chiral Lanthanide Complexes

Remarkably high asymmetric amplifications (positive nonlinear effects) were realized in some chiral lanthanide complex-catalyzed organic reactions such as the asymmetric hetero-Diels–Alder reaction, Michael addition reaction, epoxidation, etc. These phenomena may be explained by the autogenetic formation of the enantiopure lanthanide complexes as the most active catalysts. The high coordination numbers of the lanthanides seem to play an important role through the formation of aggregates of the heterochiral complexes as less active catalysts.     

Asphaltenes Flocculation in Light Crude Oils: A Chemical Approach to the Problem

This article describes the state‐of‐the‐art of the phenomena associated to the flocculation and precipitation of asphaltenes as well as the solutions used to prevent this kind of phase behavior problem in a Brazilian light (42⁰ API) crude oil. A discussion on how to diagnose this light crude tendency to flocculate its low concentration (0.3%) asphaltenes and on the approach to (chemically) mitigate the phenomena also are provided. To address the problem a comprehensive study was carried out as follows: 1) Scoping trials to assess the so‐called asphaltenes deposition envelope (ADE) of the crude, a key parameter to design the chemical injection system and to production management. To accomplish that a mono‐phase crude oil sample was collected and tests were performed on a PVT cell equipped with a solid detection system. These PVT results enabled us to evidence the reversibility of the asphaltenes flocculation process—above the bubble point pressure—which is in agreement with the Hildebrand theory for macromolecules in hydrotopic solutions and; 2) A suite of field experiments to address the following issues: asphaltenes flocculation inhibitor dosage optimization; how to collect inhibitor‐free oil samples for well site evaluation; adaptation of the existing analytical methods for well site analysis and: setting up guidelines against which measure the inhibitor performance in this low‐asphaltenes concentration crude oil.

The engineered solutions that ended up being developed from this comprehensive study are now incorporated to Petrobras flow assurance solutions portfolio.     

十六烷基三甲基溴化铵修饰P型沸石吸附水中直链烷基苯磺酸钠的研究

通过使用碱液对天然斜发沸石(Z)进行处理制得P型沸石(PZ), 再用十六烷基三甲基溴化铵(CTMAB)对Z和PZ进行修饰, 制得有机改性沸石ZC和PZC, 对比考察了ZC和PZC对直链烷基苯磺酸钠(LAS)的吸附性能. 实验结果表明, 制得的PZ硅/铝比为2, 比Z(4.85)降低58.8%; PZ的零净电荷点、 比表面积、 孔径和孔容均高于Z; 吸附平衡时间为4 h. 当pH=2时, ZC和PZC对LAS吸附量达到最高, 吸附数据符合Langmuir准二级动力学方程和Langmuir等温吸附方程, 饱和吸附量(q_m)分别为12.658和27.100 mg/g, 吸附过程主要为单分子层的化学吸附, PZC的吸附速率常数大于ZC, 具有更好的动力学性能.     

Pure Blue‐Light Emissive Poly(oligofluorenes) with Bifunctional POSS in the Main Chain

Emission of conjugated polymers is known to undergo bathochromic shift from solution to film formation due to π–π stacking in the solid state. In this report, a series of pearl‐necklace‐like hybrid polymers is designed via the hydrosilylation condensation between bifunctional polyhedral oligomeric silsesquioxanes ( B‐POSS ) and oligofluorene segments. Optoelectronic analyses unequivocally show that the presence of these interconnecting B‐POSS can effectively reduce red‐shift in photoluminescence and electroluminescence during film formation. These hybrid poly(oligofluorenes) display stable blue emission with high color purity. Thermal analyses also indicate that they are vitrified polymers with high glass transition temperature (up to 125 °C). We believe that this strategy can be extended to other conjugated systems to control color purity in electroactive materials and holds promise as new emissive materials for various applications.

     

羧基化碳纳米管存在下茜素红-蛋白质的光散射光谱研究

本文报道了羧基化碳纳米管存在下茜素红-蛋白质的光散射光谱。与无羧基化碳纳米管时相比,其散射光强度明显增加。优化了影响体系光散射检测的实验参数。在实验选定最佳条件下,考察了散射光强度与蛋白质浓度的关系,发现在362 nm波长处散射光强度与牛血清蛋白(BSA)和人血清蛋白(HSA)浓度均在0.10～9.0 mg/L范围内呈线性关系,其检出限为0.053 mg/L。将该法用于人血清总蛋白含量的测定,结果令人满意。     

络合剂作用下光催化氧化纳米铁氧化物的生成及机理

进行了空气氧化Fe(OH)₂悬浮液, 络合剂(乙二胺、草酸、柠檬酸)作用下光催化氧化制备FeOOH的研究. 结果表明: 在室光下, 一定量乙二胺、草酸、柠檬酸的加入有利于纯γ-FeOOH的生成; 且随光强的增强, γ-FeOOH的晶化性降低. 机理分析表明: 可见光存在下, 络合剂的加入, 不仅使中间物绿锈GR(II)结晶度变差, 溶解加快; 而且络合剂与Fe^2＋形成的配合物可吸收部分可见光, 生成强氧化型的自由基, 使反应初期Fe^2＋快速氧化为Fe^3＋, 快的氧化速度利于生成低晶化度的γ-FeOOH.     

新的含大体积取代基的β-氨基醇配体的合成及在二乙基锌对芳香醛的不对称加成反应中的应用

以L-脯氨酸为起始原料,两个在其羟基所在的α-C上具有大体积取代基的β-氨基醇配体被简便地合成出来,并被用于催化二乙基锌对醛的不对称加成,得到了ee值较高的S构型的手性二级醇.结果显示更大体积取代基团的氨基醇配体并不能够获得更高的对映选择性.     

New Promises and Opportunities in 3D Printable Inks Based on Coordination Compounds for the Creation of Objects with Multiple Applications

This review focuses on the usefulness of coordination bonds to create 3D printable inks and shows how the union of chemistry and 3D technology contributes to new scientific advances, by allowing amorphous or polycrystalline solids to be transformed into objects with the desired shape for successful applications. The review clearly shows how there has been considerable increase in the manufacture of objects based on the combination of organic matrices and coordination compounds. These coordination compounds are usually homogeneously dispersed within the matrix, anchored onto a proper support or coating the printed object, without destroying their unique properties. Advances are so rapid that today it is already possible to 3D print objects made exclusively from coordination compounds without additives. The new printable inks are made mainly with nanoscale nonporous coordination polymers, metal–organic gels, or metal–organic frameworks. The highly dynamic coordination bond allows the creation of objects, which respond to stimuli, that can act as sensors and be used for drug delivery. In addition, the combination of metal–organic frameworks with 3D printing allows the adsorption or selective capacity of the object to be increased, relative to that of the original compound, which is useful in energy storage, gas separation, or water pollutant elimination. Furthermore, the presence of the metal ion can give them new properties, such as luminescence, that are useful for application in sensors or anticounterfeiting. Technological advances, the combination of various printing techniques, and the properties of coordination bonds lead to the creation of surprising, new, printable inks and objects with highly complex shapes that will close the gap between academia and industry for research into coordination compounds.     

HPLC with polysaccharide chiral stationary phase in polar‐organic phase mode: Application to the asymmetric epoxidation of allylic alcohols

A simple and rapid HPLC method using a polysaccharide‐based chiral stationary phase (Chiralpak AD‐H) in polar‐organic phase mode has been developed for direct resolution of glycidyl nitrobenzoate (GNB) and 2‐methyl glycidyl nitrobenzoate (MGNB) enantiomers. ACN and methanol were used as mobile phase and the effects of the addition of ethanol and 2‐propanol as organic modifier in the mobile phase, flow rate and the column temperature were tested. The optimized conditions were: methanol/ethanol (80:20) at a flow rate of 0.9 mL/min and 40°C. Analysis time was ?13 min and the chiral resolution was ?2. The method was validated and resulted to be selective, precise and accurate. The method was found to be linear in 2–300 μg/mL range (R² >0.999) with an LOD nearly 0.5 μg/mL for four enantiomers. GNB and MGNB enantiomers were obtained by asymmetric epoxidation of allyl alcohol and 2‐methyl allyl alcohol, respectively, using chiral titanium–tartrate complexes as catalyst and dichloromethane as solvent after in situ derivatization of the intermediate glycidols derivatives. The quite simple and rapid validated method was applied successfully for direct determination of the enantiomeric excess (?90%) and yield obtained in real samples of asymmetric epoxidation of allylic alcohols without further purification, workup or solvent removal. The method provides a useful and value‐added tool for controlling the enantiomeric purity of the synthesized epoxides.     

A new and efficient aerobic oxidation of aldehydes to carboxylic acids with singlet oxygen in the presence of porphyrin sensitizers and visible light

A new aerobic route is introduced for the oxidation of a variety of aromatic and aliphatic aldehydes to the corresponding carboxylic acid derivatives using molecular oxygen in the presence of tetraphenylporphyrin (H₂TPP), tetramesitylporphyrin (H₂TMP), tetrakisdichlorophenylporphyrin (H₂TDCPP), ZnTPP, and ZnTMP as sensitizers using visible light in an organic solvent. The method has a wide range of applications, does not involve cumbersome work-up, exhibits chemoselectivity, and proceeds under mild reaction conditions. The products are obtained with good conversions and in reasonable reaction times.     

Photopolymerization of Butyl Methacrylate in the Presence of Nanoparticles of ZnO,Sensitized to Visible Light with Xanthene Dyes

The photopolymerization of butyl methacrylate in isopropanol with participation of nanoparticles of wide-gap semiconductor ZnO has been studied. The possibility of sensitizing ZnO nanoparticles to visible light with a series of halogenated fluoresceins has been established. The rate of photoinitiation of polymerization in the systems studied is principally determined by the rate of electron transfer from the photoexcited molecule of the sensitizer into the conduction zone of the semiconductor nanoparticles.     

Photo Catalytic Degradation of Azo Dyes over Mn2+ Doped TiO2 Catalyst under UV/Solar Light:An Insight to the Route of Electron Transfer in the Mixed Phase of Anatase and Rutile

Mn²⁺ ion was doped into the TiO₂ matrix and its photocatalytic activity was evaluated for the degradation of a mono azo dye methyl orange (MO) and a di‐azo dye brilliant yellow (BY) under UV/solar light. X‐ray diffraction results revealed the phase transformation from anatase to rutile due to the inclusion of Mn²⁺ ion into the TiO₂ matrix. All the doped catalysts showed a red shift in the band gap to the visible region. The degradation reaction of the dyes was found to be dependent on its structure. It was found that mono azo dye degrades faster than di azo dye under UV/solar light. The rate constant under identical conditions calculated for the degradation of MO is 2.4 times (under UV light) and 4.5 times (under solar light) higher compared to BY. Among the photocatalysts studied, Mn²⁺(0.06 at.%)‐TiO₂ showed higher activity under both UV and solar light illumination. The synergestic effect in the bicrystalline framework of anatase and rutile effectively suppresses the charge carrier recombination and enhances the photocatalytic activity. The degradation reaction was followed by UV‐visible spectroscopy and the photoproducts formed were analyzed by GC‐MS techniques.