Synthesis,characterization and application of alumina/ vanadium pentoxide nanocomposit by sol–gel method

In this work, we report the preparation of Al₂O₃/V₂O₅ nanocomposit using vanadium and aluminum nitrate by sol–gel method. Characterization of nanocomposit was carried out by powder X‐ray diffractometry (XRD), Fourier transform infrared (FT‐IR), scanning electron microscopy (SEM), Energy‐Dispersive X‐ray (EDX) and UV spectroscopy. Then, applicability of the synthesized nanocomposit was tested as a nanocatalyst for the synthesis of diindolyl oxindole derivatives, an important class of potentially bioactive compounds. The products were obtained in good to high yields from one‐pot three‐component condensation of isatin with indole. Also, this nanocatalyst has been reused several times, without observable loss of activity.     

Study on the mechanism of catalytic synthesis of dimethyldichlorosilane by AlCl3/MIL‐53(Al)@γ‐Al2O3

Dimethyldichlorosilane, one of the most consumed organosilicon monomers in the industry, can be prepared in a highly efficient and environmentally friendly synthesis method of disproportionating methylchlorosilanes. However, the internal mechanism of the reaction remains unclear. In this paper, the mechanism catalyzed by AlCl₃/MIL‐53(Al) and AlCl₃/MIL‐53(Al)@γ‐Al₂O₃ catalysts was calculated at B3LYP/6‐311++G(3df, 2pd) level by using the density functional theory (DFT). The results showed that although the two catalysts had similar active structures, the catalytic effects were significantly different. The Lewis acid center on the surface of γ‐Al₂O₃ in the core‐shell catalyst is complementary to the classic Lewis acid AlCl₃ through the spatial superposition effect, which greatly improves the Lewis acid catalytic activity of AlCl₃/MIL‐53(Al)@γ‐Al₂O₃.     

Highly efficient regioselective ring openings of N-tosylaziridines to haloamines using ferric(Ⅲ) halides

FeX3（X = Cl, Br） were found to be very effective reagents and powerful catalysts for regioselective ring openings of a variety of N-tosylaziridines with them to afford the corresponding b-haloamines in good to excellent yields with high regioselectivity under mild conditions. At the same time, 13 new compounds were obtained firstly. Moreover, the b-bromoamine prepared could be transferred into b-nitroamine with NaNO2 in moderate yield.     

Er3+单掺、Er3+/Yb3+共掺杂Ca12Al14O32F2的 制备及上转换发光性质

利用高温固相法成功制备了Er~(3+)单掺、Er~(3+)/Yb~(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2上转换发光样品。在980 nm激光激发下,Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺杂样品均呈现出较强的绿光(528,549 nm)和较弱的红光(655 nm)发射,分别归因于Er~(3+)离子的~2H_(11/2),~4S_(3/2)→~4I_(15/2)和~4F_(9/2)→~4I_(15/2)能级跃迁。随着Er离子浓度的增加,单掺杂样品上转换发光强度先增大后减小,最佳掺杂浓度为0.8%。共掺杂Yb~(3+)后,Er~(3+)的发光强度明显增大。还原气氛下合成的样品上转换发光强度增大约两倍,可能和笼中阴离子基团变化有关。发光强度和激发光功率的关系表明所得上转换发射为双光子吸收过程,借助Er~(3+)-Yb~(3+)体系能级结构详细讨论了上转换发射的跃迁机制。     

Adsorption of Eu(III) on titanate nanotubes studied by a combination of batch and EXAFS technique

The effects of pH,contact time and natural organic ligands on radionuclide Eu(Ⅲ) adsorption and mechanism on titanate nanotubes(TNTs) are studied by a combination of batch and extended X-ray absorption fine structure(EXAFS) techniques.Macroscopic measurements show that the adsorption is ionic strength dependent at pH < 6.0,but ionic strength independent at pH > 6.0.The presence of humic acid(HA) /fulvic acid(FA) increases Eu(Ⅲ) adsorption on TNTs at low pH,but reduces Eu(Ⅲ) adsorption at high pH.The results of EXAFS analysis indicate that Eu(Ⅲ) adsorption on TNTs is dominated by outer-sphere surface complexation at pH < 6.0,whereas by inner-sphere surface complexation at pH > 6.0.At pH < 6.0,Eu(Ⅲ) consists of ～ 9 O atoms at REu?O ≈ 2.40  in the first coordination sphere,and a decrease in NEu-O with increasing pH indicates the introduction of more asymmetry in the first sphere of adsorbed Eu(Ⅲ).At long contact time or high pH values,the Eu(Ⅲ) consists of ～2 Eu at REu-Eu ≈ 3.60  and ～ 1 Ti at REu-Ti ≈ 4.40 ,indicating the formation of inner-sphere surface complexation,surface precipitation or surface polymers.Surface adsorbed HA/FA on TNTs modifies the species of adsorbed Eu(Ⅲ) as well as the local atomic structures of adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids.Adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids forms both ligand-bridging ternary surface complexes(Eu-HA/FA-TNTs) as well as surface complexes in which Eu(Ⅲ) remains directly bound to TNT surface hydroxyl groups(i.e.,binary Eu-TNTs or Eu-bridging ternary surface complexes(HA/FA-Eu-TNTs)).The findings in this work are important to describe Eu(Ⅲ) interaction with nanomaterials at molecular level and will help to improve the understanding of Eu(Ⅲ) physicochemical behavior in the natural environment.     

Metal–organic framework of amine‐MIL‐53(Al) as active and reusable liquid‐phase reaction inductor for multicomponent condensation of Ugi‐type reactions

Metal–organic framework of NH₂‐MIL‐53(Al), with coordinative unsaturated aluminium sites, has been shown to be active in the Groebke–Blackburn–Bienaymé multicomponent coupling reaction based on Ugi‐type amine and aldehyde condensation over isocyanide and then a cyclization process. Interestingly this reaction occurred under solvent‐free conditions with high yield, in which the NH₂‐MIL‐53(Al) could be recovered and reused for five reaction cycles, giving a total turnover number of 455.     

Multidimensional space groups: Tables and standards

The previous speakers have dealt with tangible physical objects; I am to deal with organizational and symbolic problems. The symbolic problems are of greater scientific importance, but I must begin with those of human organization and in particular with the structure of the International Union of Crystallography (acronym IUCr).     

Cross section of the impact single ionization of B2＋ by H＋

The ionization process of B2+ by H+ impact is studied using the continuum-distorted-wave eikonal-initial-state (CDW-EIS) method and the modified free electron peak approximation (M-FEPA), respectively. Total, single-, and double- differential cross sections from 1s and 2s orbitals are presented for the energy range from 10 keV/u to 10 MeV/u. Comparison between the results from the two methods demonstrates that the total and single-differential cross sections for the high-energy incident projectile case can be well evaluated using the simple M-FEPA model. Moreover, the M-FEPA model reproduces the essential features of the binary-encounter (BE) bump in the double-differential cross sections. Thus, the BE ionization mechanism is discussed in detail by adopting the M-FEPA model. In particular, the double- and single-differential cross sections from the 2s orbital show a high-energy hip, which is different from those from the 1s orbital. Based on Ref. [1], the Compton profiles of B2+ for 1s and 2s orbitals are given, and the hips in DDCS and SDCS from the 2s orbital are explained.     

Structural,optical and photocatalytic properties of (Mg,Al)-codoped ZnO powders prepared by sol–gel method

Structural and optical properties of 1 at % Al-doped Zn_1−xMg_xO (x=0–8%) powders prepared by sol–gel method were systematically investigated by means of X-ray diffraction, scanning electron microscopy, ultraviolet–visible absorbance measurement, photoluminescence and Raman scattering spectra. All the powders retained the hexagonal wurtzite structure of ZnO. The band gap and near band emission energies determined from absorbance and photoluminescence spectra increased linearly with increasing Mg content, respectively, which implied that the Mg worked effectively on ZnO band gap engineering, irrespective of Al codoping. However, according to the PL and Raman scattering studies, for the sample of x=8%, the Al doping efficiency was decreased by higher Mg codoping. On the other hand, the effect of Mg codoping on photocatalytic degradation of methylene orange was explored experimentally. The substitution of Mg ions at Zn sites shifted the conduction band toward higher energies and then enhanced the photocatalytic activity, while the incorporation of interstitial Mg ions and decreased Al doping efficiency for higher Mg doping sample (x=8%) reduced the photocatalytic activity.