Premodification of Pt/γAl2O3 with Cinchonidine for the Enantioselective Hydrogenation of Ethyl Pyruvate: Effect of Premodification Conditions on Reaction Rate and Enantioselection

The premodification of a 5 wt% Pt/-Al₂O₃ catalyst with cinchonidine (0.01 and 0.2 g g^-1 _catalyst) is described and discussed. Premodification is carried out by treating the catalyst with a solution of cinchonidine followed by solvent removal. Catalysts premodified in this way give the same ee and initial rate of reaction for the enantioselective hydrogenation of ethyl pyruvate as those using the standard in situ modification procedure. Investigations of different solvents for premodification and reaction (dichloromethane, ethanol) show that it is the solvent used for the reaction that controls the observed enantioselection. Premodified catalysts also display the initial transient behavior typically observed with in situ modified catalysts in which the ee increases with conversion in the early part of the reaction. Premodified catalysts show an enhanced rate of reaction when ethanol is used as the reaction solvent compared with in situ modified catalysts under the same conditions. Premodification using aerobic conditions gives the best results and premodified catalysts can be stored prior to use for up to a week without loss of catalytic performance.     

Role of La2O3 in Pd-Supported Catalysts for Methanol Decomposition

Systems of Pd supported on various La₂O₃-modified -Al₂O₃ and CeO₂–Al₂O₃ catalysts were tested for catalytic methanol decomposition and characterized by means of XRD, BET, TPR, H₂-chemisorption and CO–FTIR. The addition of lanthanum significantly improved the selectivity of CO and H₂ for all the catalysts but showed a different influence on the catalytic activity in two systems. Methanol conversion decreased on La₂O₃-modified Pd/-Al₂O₃ catalysts, in line with the reduction of Pd dispersion, while the addition of La₂O₃ improved the dispersion of Pd and reinforced Pd–CeO₂ interaction for La₂O₃-modified Pd/CeO₂–Al₂O₃ catalysts, which resulted in a high production rate of CO and H₂. Thus, a synergistic effect between CeO₂ and La₂O₃ was observed on -Al₂O₃-supported Pd catalyst for methanol decomposition.     

Deformation Dynamics of a Reactive Medium During Gasless Combustion

Deformation during gasless combustion of 5Ti + 3Si and Ti + C samples was studied experimentally. The dynamics of motion of the material in a gasless combustion wave was studied using highspeed video recording (500 frames/sec) with a spatial resolution of the order of 10 m. It was shown that behind the combustion front, the medium was first expanded and then compressed. The dimensions of the expansion and compression zones were determined.     

Long-term residual value of North Carolina and Queensland rock phosphates compared with triple superphosphate

The effectiveness of large single applications of North Carolina reactive rock phosphate, Queensland non-reactive rock phosphate, and Calciphos, were compared to the effectiveness of superphosphate in field experiments in south-western Australia for up to 11 years after application. As measured using plant yield, superphosphate was the most effective fertilizer in the year of application, and relative to freshly-applied superphosphate, the effectiveness of the superphosphate residues declined to be about 15 to 65% as effective in the year after application, and 5 to 20% as effective 9 to 10 years after application. Relative to freshly-applied superphosphate, all the rock phosphates were 10 to 30% as effective in the year of application, and the residues remained 2 to 20% as effective in the 10 years after application. The bicarbonate soil test reagent predicted a more gradual decrease in effectiveness of superphosphate of up to 70% 10 years after application. For rock phosphate, the reagent predicted effectiveness to be always lower than for superphosphate, being initially 2 to 11% as effective in the year after application, and from 10% to equally as effective 10 years later. Therefore rock phosphates are unlikely to be economic alternatives to superphosphate in the short or long term on most lateritic soils in south-western Australia.     

Lowland rice response to potassium fertilization and its effect on N and P uptake

Not much is known about the response of lowland rice to K fertilization under Brazilian conditions. A field experiment was conducted during four consecutive years to determine the response of three lowland rice (Oryza sativa L.) cultivars to K fertilization on a Low Humic Gley soil. In the first two years, K was broadcast at rates of 0, 42, 84, 126, and 168 kg K ha^–1. In the last two years K rates were reduced to 0, 25, 50, 75, and 100 kg K ha^–1 and applied in a band. Potassium significantly (P < 0.01) increased grain yields but the response varied from cultivar to cultivar and year to year. Yield responses to K fertilization were superimposed on a general trend of increasing grain yields across the four growing seasons. Mean grain yields increased 14.3% with broadcast application of K in the first two years and 10.4% with banded application of K in the last two years when compared to the control treatments. Extractable soil K increased with K application rate and decreased with soil depth. Potassium was rapidly removed from the soil and yearly broadcast or banded application of K can be expected to result in a significant increase in grain yield of lowland rice in these soils.     

锂离子电池正极材料LixMn2O4研究进展

总结了锂离子电池正极材料LixMn2O4的合成方法，归纳了造成容量衰减问题的原因和目前为解决该问题所采用的各种方法，并且对下一步的研究工作进行了展望。     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

基于云计算的去小型机研究

基于对R1SC和x86CPU的分析,结合大量的研究数据,研究了去小型机的必要性和可能性。通过分析可以清晰认识到,x86服务器已经从性能、可靠性、可用性、服务能力等方面全面满足云计算的需求。     

Suppression of the α → β-nickel hydroxide transformation in concentrated alkali: Role of dissolved cations

The presence of dissolved cations such as Al and Zn in alkaline electrolyte (6 M KOH) suppresses the -nickel hydroxide transformation. The uptake of Al (10 mol%) and Zn (30 mol%) exhibited by the active material likely stabilizes the -phase. Dissolved Al is deleterious to the performance of the nickel hydroxide electrode, whereas, dissolved Zn enhances the specific discharge capacity of nickel hydroxide by approximately 25% showing that the mode of metal uptake is different in the two cases.     

Effect of structural and electrochemical properties of different Cr-doped contents of Li[Ni1/3Mn1/3Co1/3]O2

Layered Li[Ni_(1−x)/3Mn_(1−x)/3Co_(1−x)/3Cr_x]O₂ materials with x = 0, 0.01, 0.02, 0.03, 0.05 are prepared by a solid-state pyrolysis method. The oxide compounds were calcined with various Cr-doped contents, which result in greater difference in morphological (shape, particle size and specific surface area) and the electrochemical (first charge profile, reversible capacity and rate capability) differences. The Li[Ni_(1−x)/3Mn_(1−x)/3Co_(1−x)/3Cr_x]O₂ powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry, and SEM. XRD experiment revealed that the Li[Ni_(1−x)/3Mn_(1−x)/3Co_(1−x)/3Cr_x]O₂ (x = 0, 0.01, 0.02, 0.03, 0.05) were crystallized to well layered -NaFeO₂ structure. The first specific discharge capacity and coulombic efficiency of the electrode of Cr-doped materials were higher than that of pristine material. When x = 0.02, the sample showed the highest first discharge capacity of 241.9 mAh g⁻¹ at a current density of 30 mA g⁻¹ in the voltage range 2.3–4.6 V, and the Cr-doped samples exhibited higher discharge capacity and better cycleability under medium and high current densities at room temperature.