电氧化N_2O_4制备N_2O_5工艺研究

以N2O4和HNO3为原料,通过电氧化法制备了新型绿色硝化剂N2O5,并研究了电解氧化法制备N2O5工艺的影响因素,主要讨论了电解反应时间、电流密度和反应温度对该工艺的影响。在反应时间为4～5h,电流密度为0.09～0.10A/cm2,反应温度为5～10℃时,可得到质量分数较高的N2O5阳极液。     

N2,N2,N6,N6-四乙基-4-醛基吡啶-2,6-二甲酰胺的合成

以2,6-二甲基吡啶为原料,经KMnO4氧化、二乙胺酰胺化、吡啶环自由基亲核取代反应得到N2,N2,N6,N6-四乙基-4-羟甲基吡啶-2,6-二甲酰胺,然后用Sarret试剂氧化得到标题化合物并探讨了氧化反应的最佳条件,产物结构经1HNMR、IR和MS得到表征.该产物是合成新型吡啶类有机配体的重要中间体.     

Synthesis and nanostructure of [Mo(C6H4O2)3]·2(C4H8N2O) and the synthesis from 1,2-PDA to (C4H8N2O)

Continuing our work on the synthesis of MoO₂L₂ and MoO₃L_AL_B that show excellent anti-cancer activities in vitro, the MoL₃ have been synthesized by the solvothermal reaction of Na₂MoO₄ with catechols and 1,2-DPA in the mixed solvent of MeCN/MeOH. X-ray diffraction revealed that Mo in chiral octahedral geometry coordinate with three catechol ligands formed three five-membered rings, and the [Mo(C₆H₄O₂)₃] are linked by hydrogen bonds Mo(OC₆H₄)O…H–N(C₄H₈O)N–H…O(C₆H₄O)Mo through the by-product (C₄H₈N₂O) that are formed by one 1,2-DPA with one CO₂ on the catalysis of Mo-complex. Also, we have disassembled bulk crystal into nano-aggregates, and under TEM mono-lamella morphology of nanostructures was observed, which agrees well with the previous conclusion that the morphologies of the nano-aggregates are associated with the quantum motifs in their crystal lattices. [Mo(C₆H₄O₂)₃] have also been characterized by UV–vis spectra, cyclic voltammogram and thermogravimetric analysis.     

三维超分子化合物[Zn(C6H4O2N)2·(H2O)4]n的水热合成及晶体结构

用2-羧基吡啶和六水合氯化锌反应制备了一种新的三维氢键超分子配合物,经X-射线衍射分析确定了单晶结构.该晶体属单斜晶系,P2(1)/n空间群,晶胞参数为a=9.836(2)(A),b=5.2256(10)(A),c=14.611(3)(A),Mr=381.64,β=90.01(3)°,V=751.0(3)(A)3,Z=2,Dc=1.688Mg·m-3,F(000)=392,μ=1.680mm-1,R=0.0258,wR=0.0612.共收集2159个衍射数据,其中1273个为独立衍射点(Rint=0.0332),可观测点数1139个(I＞2σ(I)).结果表明,在组成该超分子体系的基本结构单元[Zn(C6H4O2N)2·(H2O)4]中,Zn(Ⅱ)离子形成六配位的畸变的八面体构型,配合物单元之间通过氢键OH…O相互连接,形成了无限延伸的具有网状结构的三维超分子体系.     

Effects of N management on N2O and CH4 fluxes and15N

Forage production in irrigated mountain meadows plays a vital role in the livestock industry in Colorado and Wyoming. Mountain meadows are areas of intensive fertilization and irrigation which may impact regional CH₄ and N₂O fluxes. Nitrogen fertilization typically increases yields, but N-use efficiency is generally low. Neither the amount of fertilizer-N recovered by the forage nor the effect on N₂O and CH₄ emissions were known. These trace gases are long-lived in the atmosphere and contribute to global warming potential and stratospheric ozone depletion. From 1991 through 1993 studies were conducted to determine the effect of N source, and timing of N-fertilization on forage yield, N-uptake, and trace gas fluxes at the CSU Beef Improvement Center near Saratoga, Wyoming. Plots were fertilized with 168 kg N ha^-1. Microplots labeled with¹⁵N-fertilizer were established to trace the fate of the added N. Weekly fluxes of N₂O and CH₄ were measured during the snow-free periods of the year. Although CH₄ was consumed when soils were drying, flood irrigation converted the meadow into a net source of CH₄. Nitrogen fertilization did not affect CH₄ flux but increased N₂O emissions. About 5% of the applied N was lost as N₂O from spring applied NH₄NO₃, far greater than the amount lost as N₂O from urea or fall applied NH₄NO₃. Fertilizer N additions increased forage biomass to a maximum of 14.6 Mg ha^-1 with spring applied NH₄NO₃. Plant uptake of N-fertilizer was greater with spring applications (42%), than with fall applications (22%).     

Bi-Co3O4 catalyzing N2O decomposition with strong resistance to CO2

Bi added to Co₃O₄ by coprecipitation method significantly decreased the average crystalline size of Co₃O₄ and increased the surface area and the active sites of the catalyst in population for catalyzing the N₂O decomposition. Over Bi_0.02Co that was the optimized from the Bi_xCo catalysts, 2000 ppm of N₂O in pure Ar was completely decomposed at 400 °C in GHSV of 20,000 h^− 1. Outstandingly, the catalyst exhibited a strong resistance to CO₂, stable N₂O conversion larger than 95% was obtained over the catalyst in the presence of 10% CO₂ at the reaction temperature.     

Synthesis and Properties of Bi2Fe4O9 with FeCl2·6H2O Addition

Single‐phase Bi₂Fe₄O₉ is synthesized successfully by the solid‐state reaction technique with FeCl₂·6H₂O additives. The two optical band gaps, and the iron ion's chemical valence state both decrease with the addition of FeCl₂·6H₂O, which may be attributed to the decrease in the split energy of iron 3d orbital.     

Absorption of NO2/N2O4 in nitric acid

Laboratory-scale measurements were performed on the absorption of NO₂ gas into diluted nitric acid. The concentration of NO₂ gas, which represents an NO₂/N₂O₄ equilibrium, varied from 1000 to 20000 ppm, the carrier gas being nitrogen. The concentration of nitric acid ranged from 15 to 60 mass-%. The absorption experiments were carried out in a double stirred cell, with a defined gas/liquid interface as the mass transfer area. The liquid phase was conducted periodically and the gas phase continuously. Mass flow rates were determined. The well-known film model of absorption was used for analyzing the experimental results. Only the N₂O₄ species was considered to pass the gas/liquid interface. The measured data yielded values of H(k D₁)^1/2 as well as their variation with temperature and nitric acid concentration.     

Experimental investigation of the LiAlSi2O6‐MgSiO3 and LiAlSi2O6‐CaMgSi2O6 isopleths at 1 atm

The phase diagrams of the LiAlSi₂O₆‐MgSiO₃ and LiAlSi₂O₆‐CaMgSi₂O₆ isopleths were experimentally investigated at 1 atm using the quenching method and differential scanning calorimetry and the phases produced were characterized with the help of X‐ray diffraction and electron probe microanalysis. With the help of thermodynamic optimization, the phase diagrams of both systems were more accurately reported. No detectable solubility of Li₂O in diopside and enstatite was found. However, both systems are not simple binary eutectic systems because their phase equilibria are somewhat complex due to the presence of some β‐spodumene solid solution. In the β‐spodumene solid solution, no notable solubility of MgO and CaO was detected; evidence of significant solubility of SiO₂ was confirmed.     

MnS_2O_6－MnSO_4－H_2O水盐体系相平衡研究

用湿渣法测定了ＭｎＳ２Ｏ６－ＭｎＳＯ４－Ｈ２Ｏ三元水盐体系在１０℃和５０℃下的相图，并提出从该体系中分离出ＭｎＳ２Ｏ６和ＭｎＳＯ４的途径。     

Catalytic reduction of N2O with CH4 and C3H6 over Ag–Rh/Al2O3 bimetallic catalyst in the presence of oxygen

A study of nitrous oxide (N₂O) reduction with methane (CH₄) and propene (C₃H₆) in the presence of oxygen (5%) over Ag/Al₂O₃, Rh/Al₂O₃ and Ag–Rh/Al₂O₃ catalysts, with Ag and Rh loadings of 5 wt% and 0.05 wt% respectively, has been performed. From the results, it was observed that the Ag–Rh bimetallic catalyst was the most active for both nitrous oxide removal (more than 95%) and hydrocarbon oxidation. This high activity seems to be connected with a synergistic effect between Ag and Rh. The findings from X‐ray diffraction and X‐ray photoelectron spectroscopy studies showed also, that there were no strong interactions (eg alloying) between Ag and Rh. Copyright © 2005 Society of Chemical Industry     

MnS_2O_6－MnSO_4－H_2O水盐体系相平衡研究

用湿渣法测定了ＭｎＳ２Ｏ６－ＭｎＳＯ４－Ｈ２Ｏ三元水盐体系在１０℃和５０℃下的相图，并提出从该体系中分离出ＭｎＳ２Ｏ６和ＭｎＳＯ４的途径。