Role of Microstructure and Spectrum Features on the Catalysis Effect of Ce1-x(Nd0.5Eu0.5)xO2-δSolid Solutions

Nanosized Ce^1-x）（Nd^0.5）Eu^0.5））xO^2-δ） solid solutions（x = 0.00-0.20） were synthesized by means of hydrothermal method.Then the solid solutions were ball milled with Mg2Ni and Ni powders for 20 h to get the Mg2Ni–Ni–5 mol% Ce^1-x）（Nd^0.5）Eu^0.5））xO^2-δ） composites.The structures and spectrum characteristics of the Ce^1-x）（Nd^0.5）Eu^0.5））xO^2-δ） solid solutions catalysts were analyzed systemically.XRD results showed that the doped samples exhibited single phase of CeO2 fluorite structure.The cell parameters and cell volumes were increased with increasing the doped content.Raman spectrum revealed that the peak position of F^2g mode shift to higher wavenumbers and the peak corresponding to oxygen vacancies were observed distinctly for the doped samples.UV-Vis technique indicated that the absorption peaks of Eu^3＋ and Nd^3＋ ions appeared; the bandgap energy was decreased linearly.The electrochemical and kinetic properties of the Mg2Ni–Ni–5 mol% Ce1-x（Nd0.5Eu0.5xO2-δ composites were measured.The maximum discharge capacity was increased from 722.3 mA h/g for x = 0.00 to 819.7 mA h/g for x = 0.16,and the cycle stability S20 increased from 25.0%（x = 0.00） to 42.2%（x = 0.20）.The kinetic measurement proved that the catalytic activity of composite surfaces and the hydrogen diffusion rate were improved for the composites with doped catalysts,especially for the composites with x = 0.16 and x = 0.20.The catalysis mechanism was analyzed from the point of microstructure and spectrum features of the Ce1-x（Nd0.5Eu0.5）xO2-δ solid solutions.

Stability Studies of Lysine Acetylsalicylate(Aspirin Derivative):Mechanisms of Hydrolysis

To control the stability of the lysine acetylsalicylate compound (LAS) in aqueous solution, some studies of the hydronium ion-catalyzed, hydroxide ion-catalyzed, and spontaneous reactions of this active ingredient in water solutions have been carried out. The pH-rate profile (log kobs = f(pH)), shows that the hydrolysis reaction of the LAS, is conducted by a catalysis acid-base mechanism, with multiple reaction pathways. The rate constants, kH, kOH and k0 to the reaction pathways catalyzed by H3O+, HO– ions and to the spontaneous reaction, for the hydrolysis reaction of the reagent LAS, were determined. The results show that the studied compound LAS is unstable in basic medium and the hydrolysis reaction catalyzed by HO– ions is predominant.For a known acidity (pH ≈ 10), studies conducted for different temperatures of the medium, clearly indicate, that the experimental rate constant kobs,depends on the temperature according to the Arrhenius equation. The activation parameters: activation energy (Ea), enthalpy (ΔH≠) and entropy (ΔS≠), for the transition state were determined, The very negative value obtained for the activation parameter ΔS*, first indicates that in the transition state there is gain in order, then this late state, resembles the products and that probably for the mechanism of the LAS hydrolysis reaction catalyzed by HO– ions, the rate-determining step is a bimolecular reaction. Finally from all these results, the mechanism for the reaction pathway catalyzed by HO– ions has been elucidated.

Recent advances in the application of metal organic frameworks using in advanced oxidation progresses for pollutants degradation

Metal-organic frameworks(MOFs)materials with highly ordered and porous crystalline structure,have excellent performance in advanced oxidation progresses(AOPs)for organic contaminants degradation in water treatment.This review intends to summarize the timely references and insights for the recent advances in MOFs that are used in AOPs.Starting with the preparation methodologies,including conventional hydrothermal method,electrochemical method,sol-gel method,and emerging microwave and ultrasound assisted synthesis methods.Application and mechanism for MOFs using in various AOPs of Fenton-like,photocatalysis,catalytic ozonation,persulfate catalysis and other emerging oxidation methods are emphatically discussed.We hope this review can comprehensively summarize the research and application progress of MOFs in AOPs,deepen the understanding of the catalytic mechanisms.

PROBING THE ROLES OF DIETHYLALUMINUM CHLORIDE IN PROPYLENE POLYMERIZATION WITH MgCl_2-SUPPORTED ZIEGLER-NATTA CATALYSTS

In this article, the effect of diethylaluminum chloride （DEAC） in propylene polymerization with MgC12-supported Ziegler-Natta catalyst was studied. Addition of DEAC in the catalyst system caused evident change in catalytic activity and polymer chain structure. The activity decrease in raising DEAC/Ti molar ratio from 0 to 2 is a result of depressed production of isotactic polypropylene chains. The number of active centers in fractions of each polymer sample was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and fractionating the polymer into isotactic, medium- isotactic and atactic fractions. The number of active centers in isotactic fraction （[Ci＊]/[Ti]） was lowered by increasing DEAC/Ti molar ratio to 2, but further increasing the DEAC/Ti molar ratio to 20 caused marked increase of [Ci＊]/[Ti]. The number of active centers that produce atactic and medium-isotactic PP chains was less influenced by DEAC in the range of DEAC/Ti = 0-10, but increased when the DEAC/Ti molar ratio was further raised to 20. The propagation rate constant of Ci＊ （k^i） was evidently increased when DEAC/Ti molar ratio was raised from 0 to 5, but further increase in DEAC/Ti ratio caused gradual decrease in kpi. The complicated effect of DEAC on the polymerization kinetics, catalysis behaviors and polymer structure can be reasonably explained by adsorption of DEAC on the central metal of the active centers or on Mg atoms adjacent to the central metal

Melatonin biosynthesis pathways in nature and its production in engineered microorganisms

Melatonin is a biogenic amine that can be found in plants,animals and microorganism.The metabolic pathway of melatonin is different in various organisms,and biosynthetic endogenous melatonin acts as a molecular signal and antioxidant protection against external stress.Microbial synthesis pathways of melatonin are similar to those of animals but different from those of plants.At present,the method of using microorganism fermentation to produce melatonin is gradually prevailing,and exploring the biosynthetic pathway of melatonin to modify microorganism is becoming the mainstream,which has more advantages than traditional chemical synthesis.Here,we review recent advances in the synthesis,optimization of melatonin pathway.L-tryptophan is one of the two crucial precursors for the synthesis of melatonin,which can be produced through a four-step reaction.Enzymes involved in melatonin synthesis have low specificity and catalytic efficiency.Site-directed mutation,directed evolution or promotion of cofactor synthesis can enhance enzyme activity and increase the metabolic flow to promote microbial melatonin production.On the whole,the status and bottleneck of melatonin biosynthesis can be improved to a higher level,providing an effective reference for future microbial modification.

The formation and catalytic activity of silver nanoparticles in aqueous polyacrylate solutions

Silver nanoparticles （AgNPs） have been synthesized in the presence of polyacrylate through the reduction of silver nitrate by sodium borohydride in aqueous solution. The AgNO3 and polyacrylate carbox- ylate group concentrations were kept constant at 2.0× 10^-4 and 1.0 × 10^-2 mol·L^-1, respectively, while the ratio of [NaBH4]/[AgNO3] was varied from 1 to 100. The ultra- violet-visible plasmon resonance spectra of these solutions were found to vary with time prior to stabilizing after 27 d, consistent with changes of AgNP size and distribution within the polyacrylate ensemble occurring. These obser- vations, together with transmission electron microscopic results, show this rearrangement to be greatest among the samples at the lower ratios of [NaBH4]/[AgNO3] used in the preparation, whereas those at the higher ratios showed a more even distribution of smaller AgNP. All ten of the AgNP samples, upon a one thousand-fold dilution, catalyze the reduction of 4-nitrophenol to 4-aminophenol in the temperature range 283.2-303.2 K with a substantial induction time being observed at the lower temperatures.

Synthesis of Asymmetrical Monobenzo-Substituted Cobalt Thioporphyrazines and Their Biomimetic Catalytic Property

Two novel monobenzo porphyrazines bearing nitro and methoxyl respectively on fused benzene ring were suc- cessfully synthesized. Also, an asymmetrical porphyrazine with one butylthio branch at the pyrrolic p-position sub- stituted by hydrogen atom was successfully isolated in the course of synthesis of symmetric octakis（butylthio） porphyrazine. Their corresponding cobalt complexes were subsequently obtained and characterized. Their catalytic ability was assessed by aerobic oxidation of benzoin, showing the highest benzil yield of 95.2% for 60 min. A pos- sible mechanism was also presented from the in-situ UV-Vis spectra, in which a novel and characteristic absorption peak of metal-oxo was observed. At the same time, similar results of the extended oxidation of benzyl alcohol also confirmed the reactive mechanism.