Heterogeneous oxidation of cyclohexanone catalyzed by TS-1:Combined experimental and DFT studies

The reaction mechanism of the oxidation of cyclohexanone catalyzed by titanium silicate zeolite TS-1 using aqueous H2O2 as the oxidant was investigated by combining density function theory (DFT) calculations with experimental studies. DFT calculations showed that H2O2 was adsorbed and activated at the tetrahedral Ti sites. By taking into account the adsorption energy, molecular size, steric hindrance and structural information, a reaction mechanism of Baeyer-Villiger oxidation catalyzed by TS-1 that involves the activation of H2O2 was proposed. Experimental studies showed that the major products of cyclohexanone oxidation by H2O2 catalyzed by a hollow TS-1 zeolite wereε-carprolactone, 6-hydroxyhexanoic acid, and adipic acid. These products were analyzed by GC-MS and were in good agreement with the proposed mechanism. Our studies showed that the reaction mechanism on TS-1 zeolite was different from that on Sn-beta zeolite.     

Characterisation and coagulation performance of polysilicate-ferric-zinc

A new type of coagulant, polysilicate-ferric-zinc (PSFZn) with different Fe/Zn molar ratios, was synthesised using water glass (industrial grade, w(SiO₂) = 21 mass %, ρ = 1.34 × 10³ kg m^?3, modulus = 3.2), FeSO₄ · 7H₂O, ZnSO₄, and NaClO₃ by way of co-polymerisation in the same (Fe + Zn)/Si molar ratio based on polysilicate-ferric (PSF). The effect of the Fe/Zn molar ratios on the morphology and structure was systematically investigated using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) analysis. Three samples, namely PSFZn4, PSFZn1, and PSFZn0.25, represented Fe/Zn molar ratios of 4, 1, and 0.25, respectively, and were selected for a comparative study while a constant (Fe + Zn)/Si molar ratio equal to 1 was maintained. Accordingly, PSFZn was found to be a complex compound rather than a simple mixture of raw materials. With the decrease in Fe/Zn, a great change occurred in the surface morphology, from a tetrahedral cluster structure to a lamellar structure. The Fe—O and Fe—O—Si bonds were gradually replaced by Zn—O and Zn—O—Si. However, the crystalline peaks were more obvious with the increase in the number of zinc ions; hence the new polymer would be formed from iron, zinc, and polysilicate. In addition, the coagulation performance of PSFZn was investigated using a surface water sample. PSFZn4 exhibited a better coagulation performance than the other PSFZn coagulants. Additionally, the trends in changes in pH with different coagulation times after adding PSFZn were studied relative to PSF and FS. The replacement of zinc ions with iron ions could effectively counter the rapid decrease in pH. The effect of settling time on the coagulation efficiency was also investigated. PSFZn4 exhibited a better settlement performance than PSF and poly aluminium chloride (PAC). Hence, the partial substitution of zinc salt with iron salt not only addresses the inadequacies of iron salt but also improves the coagulation efficiency of zinc salt in water treatment.     

Chiral separation abilities of homogeneously synthesized cellulose 3,5-dimethylphenylcarbamates: Influences of degree of substitution and molecular weight

A series of cellulose 3,5-dimethylphenylcarbamates(CDMPCs) with different degrees of substitution(DS) and degrees of polymerization(DP) were homogeneously synthesized in 1-allyl-3-methylimidazolium chloride(Amim Cl). Then, the CDMPCs were coated on silica gel and used as chiral stationary phases(CSPs), and their chiral recognition abilities for seven racemates were evaluated by high performance liquid chromatography. The results showed that DS and DP of CDMPCs had a great influence on chiral recognition abilities of the CSPs. The CSPs with the DS ≈ 1 gives a low chiral recognition to most racemates. On the contrast, the CSPs with the DS ? 2 exhibited high chiral separation abilities. For example, six racemates could be separated on the CSP with CDMPC of DS ≈ 2(CSP-2). Especially, for the enantioseparation of 1-(2-naphthyl) ethanol and Tr?ger's base, CSP-2 gave the highest separation ability in all of CSPs. On the other hand, when the DP of cellulose was in a range from 39 to 220, the chiral separation abilities of CDMPCs increased as the DP increased. This work demonstrates that the structure of cellulose esters such as DS and DP has important effect on their chiral separation ability, and therefore provides a practical method to design and prepare desirable CSPs for different racemates.     

The banded spherulites of iPP induced by pressure vibration injection molding

Isotactic polypropylene(i PP) samples obtained by pressure vibration injection molding(PVIM) and conventional injection molding(CIM) were studied by polarized-light microscopy(PLM), respectively. It was found that the alternating bright and dark banded spherulites were generated in the transitional region of PVIM parts. It is the first time that the banded spherulites of isotactic polypropylene were observed in polymer processing. What's more, the banded spherulites were proved to be constituted of ?-form crystal by hot stage polarized-light microscopy(HT-PLM) and wide angle X-ray diffraction(WAXD). Morphology of the banded spherulites was also studied by scaning electronical microscopy(SEM).     

杂多酸离子液体催化燃油萃取氧化脱硫性能研究

本文首次将一系列含有不同酸性咪唑阳离子和不同杂多酸阴离子的杂多酸离子液体[C4mim]3PW12O40、[COOH-Cmim] 3PW12O40、[SO3H-C3mim]3PW12O40、[SO3H-C3mim]3PMo12O40和[SO3H-C3mim]4 SiW12O40作为催化剂,乙腈为萃取剂,H2O2为氧化剂,用于催化含二苯并噻吩、苯并噻吩及噻吩模型油的萃取氧化脱硫研究中.实验结果显示,杂多酸离子液体催化燃油脱硫性能不仅与阳离子的酸性强弱有关,而且与阴离子结构密切相关.阳离子的催化活性顺序为:[SO3H-C3mim]+＞[COOH-Cmim]+＞[C4mim]+;阴离子的催化活性顺序为PW12O403-＞ PMo12O403-＞ SiW12O404-.其中[SO3H-C3 mim]3 PW12O40催化活性最高,在60℃反应40min的条件下,二苯并噻吩的转化率约为100％,催化不同硫化物的转化率为:二苯并噻吩＞苯并噻吩＞噻吩.此外,该杂多酸离子液体循环使用5次催化活性仅略有下降.     

Ti掺杂苯基与乙基桥连的有序介孔有机硅的制备及其催化环己烯氧化反应

分别采用1,4-(双乙氧基硅烷)苯(1,4-BTEB)和1,2-三乙氧基硅基乙烷(1,2-BTESE)作为有机硅源,正硅酸乙酯(TEOS)为无机硅源,钛酸四丁酯(TBOT)为钛源,以Pluronic EO20PO70EO20(P123)为模板剂在酸性环境下水热合成制备了Ti掺杂的有机-无机有序介孔有机硅材料Ti-SBA-15-ben和Ti-SBA-15-et.同时,在合成过程中加入H2O2作为配合剂调节钛源水解速度,制备得到Ti-SBA-15-ben-H和Ti-SBA-15-et-H.采用FT-IR、DR UV-Vis、N2物理吸附、XRD、TG-DSC、TEM等方法对制备的样品进行了表征.结果表明:合成过程中加入H2O2制备的苯基桥连有机硅杂化材料具有较好的疏水性能,其骨架中活性4价位钛含量高,结构有序性最好.在以叔丁基过氧化氢(TBHP)为氧源的环己烯氧化反应中对制备的催化材料进行了对比评价,结果表明:Ti-SBA-15-ben-H表现出最高的催化活性,其催化的反应以环氧化产物为主,环己烯的转化率为26.9%,环氧选择性为32.8%,T i-SBA-15-et催化的反应以烯丙位氧化产物2-环己烯-1-酮为主,环己烯的转化率为8.5%,2-环己烯-1-酮选择性为41.2%.     

Regio‐ and Enantioselective Aza‐Diels–Alder Reactions of 3‐Vinylindoles: A Concise Synthesis of the Antimalarial Spiroindolone NITD609

An asymmetric aza‐Diels–Alder reaction of 3‐vinylindoles with isatin‐derived ketimines has been developed. A series of spiroindolone derivatives were thus obtained in good to excellent yields with excellent enantioselectivity (up to 96 % yield and 99 % ee). Furthermore, the antimalarial compound NITD609 could be obtained in three steps with an overall yield of 40.6 %. Control experiments and operando IR experiments imply a concerted reaction pathway. The regioselectivity and exo selectivity result from π–π interactions between the two indoline rings of the two reactants.     

New Cu(I) Coordination Complexes Based on Tetrathiafulvalene Substituted Triazol‐pyridine Ligand: Synthesis,Properties and Theoretical Studies

Two Cu(I) complexes based on the thioethyl‐bridged triazol‐pyridine ligand with tetrathiafulvalene unit (TTF‐TzPy, L ), [Cu(I)(Binap)(L)]BF₄ ( 5 , Binap=2,2’‐bis(diphenylphosphino)‐1,1’‐binaphthyl) and [Cu(I)(Xantphos)(L)]BF₄ ( 6 , Xantphos=9,9‐dimethyl‐4,5‐bis(diphenylphosphino)‐xanthene), have been synthesized. All new compounds are characterized by elemental analyses, ¹H NMR and mass spectroscopies. The complex 5 has been determined by X‐ray structure analyses which shows that the central copper (I) ion assumes distorted tetrahedral geometry. The photophysical, computational and electrochemical properties of L and 5 ‐ 6 have been investigated. The most representative molecular orbital energy‐level diagrams and the spin‐allowed singlet? singlet electronic transitions of the three compounds have been calculated with density functional theory (DFT) and time‐dependent DFT (TD‐DFT). The luminescence bands of Cu(I) complexes 5 ‐ 6 have been assigned as mixed intraligand and metal‐to‐ligand charge transfer ³(MLCT+π→π^*) transitions through analysis of the photophysical properties and DFT calculations. The electrochemical studies reveal that 5 ‐ 6 undergo reversible TTF/TTF^+?/TTF²⁺ redox processes and one irreversible Cu⁺→Cu²⁺ oxidation process.