Significant Decrease in Activation Temperature for the Generation of Strong Basicity: A Strategy of Endowing Supports with Reducibility.

Mesoporous solid strong bases are quite attractive due to their good catalytic performance for applications as environmentally friendly catalysts in various reactions. However, pretty harsh conditions are usually compulsory for the fabrication of strong basicity by using traditional thermal activation (e.g., 700 °C for the activation of base precursor KNO3 supported on mesoporous Al2O3). This is energy intensive and harmful to the mesoporous structure. In this study, we report a strategy of endowing supports with reducibility (ESWR) by doping low-valence Cr3+ into mesoporous Al2O3, so that the activation temperature for basicity generation is decreased significantly. Fascinatingly, KNO3 on mesoporous Al2O3 can be motivated to basic sites completely at the temperature of 400 °C via the ESWR strategy, which is much lower than the conventional thermal activation (700 °C). We have demonstrated that the redox reciprocity between KNO3 and Cr3+ is responsible for the low-temperature conversion, and Cr6+ is formed quantitatively as the oxidation product. The obtained solid bases possessing ordered mesostructure and strong basicity provide promising candidates for base-catalyzed synthesis of dimethyl carbonate via transesterification. The catalytic activity is obviously higher than a typical solid base like MgO as well as a series of reported basic catalysts containing alkali metal and alkaline-earth metal oxides.

Crystallization of new samarium polyborates.

Rare earth borates are important due to their excellent properties, especially for optics. Here, we report the hydrothermal synthesis and structural determination by single-crystal X-ray diffraction of two new samarium polyborates with layered structures, being constituted by hexaborate chains. These hexaborate chains are connected by samarium polyhedra, forming dense sheets that further interact with each other by hydrogen bonding via isolated boric acid between these sheets. The third phase possesses a three-dimensional framework structure. The thermal stability of selective samples has been studied. The crystallization of samarium borate depends highly on the experimental conditions. Three samarium polyborates have been crystallized in very similar experimental conditions, clearly indicating that new lanthanide borate compounds with tailored structures may be prepared in the future by careful choice of physicochemical conditions.

Synthesis and Properties of Moisture-Cured Reactive Polyurethane Containing Castor Oil and Oxime Compounds.

Reactive polyurethane hot-melt resin (moisture-cured reactive polyurethane, PUR) could successfully be prepared from poly(tetramethylene ether) glycol (PTMG), castor oil and dimethylglyoxime (DMG) by one or two-stage synthesis. Fourier-transform infrared spectroscopy (FTIR) analysis showed that the synthesis resins belonged to NCO-capped castor oil-based polyurethane. The thermal behaviors of the cured PUR were analyzed by differential scanning calorimeter (DSC) and dynamic mechanical analyzer (DMA) instruments. The results showed that the cured resin provided remeltable properties under the dosages of 3 wt% DMG. Furthermore, the phenomenon could be proved by FTIR analysis according to the characteristic absorption peak of NCO groups after the cured resin was heated. Comparing different syntheses, the resin prepared by one-stage synthesis showed random distribution of DMG with PUR structure and that prepared by two-stage synthesis had distribution of DMG with branching structure in the prepolymer. The former obtained lower remeltable temperatures from 90 to 130 °C than the latter temperatures, which had temperatures above 125 °C. The tensile test showed that all of the PUR films exhibited typical tough behavior. Thus, the cured resin with DMG dosages of 3 wt% provided remeltable and mechanical properties at the same time. Overall, the crosslinking density and numbers of dynamic bonds should be kept in balance for preparation of remeltable PUR.

Adsorption of nitrogen oxides by the moisture-saturated zeolites in gas stream.

This investigation examined the instantaneous adsorption of NO(x) by moisture-saturated zeolites at ambient temperature. Among the zeolites studied, Faujasite exhibited the highest adsorption capacity owing to its relatively large pore size. Besides, the influence of cation was demonstrated by comparing the adsorption of zeolites with different cation densities (NaX vs. NaY, mesoporous silica MCM-48-like vs. Faujasite) and treatments (ion exchange of NaY with Cu(2+)). For the adsorption of NO, the effects of gas flow rates and pre-adsorbed hydrocarbons such as benzene, acetaldehyde or 1,3-butadiene were evaluated. It was proven that zeolite could efficiently capture nitrogen oxides in gas stream even it had been saturated by moisture, which will be valuable for the protection of environment and public health.

Graphene sheet-starch platform based on the groove recognition for the sensitive and highly selective determination of iodide in seafood samples.

The functionalization of graphene nanosheets was realized using a simple starch mixture to achieve a highly selective recognition of iodide, thereby surmounting the complicated reactions possibly leading to low yield during functionalization. The groove recognition for starch to iodide, a novel recognition model, was established. The starch-to-graphene nanosheet mass ratio of 3:2 produced an optimal current signal. The recognition and measurement procedures were conducted in different cells, respectively. These procedures improved the selectivity and sensitivity, and overcame the possibility of interference from coexisting ions. Under optimal conditions, the graphene sheet-starch electrode was immersed in a recognition cell at pH 2.0 for 10min, afterward, in a measurement cell at pH 1.0 for quantitative analysis, resulting in the highest current signals obtained. The quantitative electrochemical measurements yielded a mean value of 214.6mg/kg in actual samples of commercially available seafood sample, whereas the spectrophotometric measurements produced a mean value of 226.7mg/kg. If the spectrophotometric value for the seafood sample is accurate, the percentage error for the electrochemical method is only 5.3%. Therefore, the electrochemical method is reliable for qualitative iodide measurements. The groove recognition was highlighted to elucidate the specific selectivity.

Improving MCM-41 as a nitrosamines trap through a one-pot synthesis.

Copper oxide was incorporated into MCM-41 by a one-pot synthesis under acidic conditions to prepare a new mesoporous nitrosamines trap for protection of the environment. The resulting composites were characterized by XRD, N2 adsorption-desorption, and H2 temperature-programmed reduction techniques, and their adsorption capabilities were assessed in the gaseous adsorption of N-nitrosopyrrolidine (NPYR). The adsorption isotherms were consistent with the Freundlich equation. The copper salt was deposited onto MCM-41 during the evaporation stage and was fixed on the host in the calcination process that followed. MCM-41 was able to capture NPYR in air below 373 K but not at 453 K. Loading of copper oxide on MCM-41 greatly improved its adsorption capability at elevated temperatures. The influence of the incorporation of copper into MCM-41 samples and the adsorption behavior of these samples are discussed in detail.