N-甲基咪唑配体络合金属Cu(Ⅰ)催化剂对水中2,4-二甲氧基溴苯还原脱溴

合成了以N-甲基咪唑为配体,Cu为活性中心的络合金属多相催化剂Cu(Ⅰ)-NHC-SBA-15.通过1H-NMR、13C-NMR、有机元素分析和FTIR对各步合成反应产物结构经行了鉴定;用SEM、N2吸附脱附等方法对催化剂进行了表征;用ICP测定了催化剂Cu含量.对催化剂催化2,4-二甲氧基溴苯还原脱溴活性进行了测试.在反应时间为24 h,通过正交实验和单因素实验,考察了催化剂用量、反应温度、还原剂用量等因素对脱溴率的影响,并确定了最佳反应条件:催化剂用量为0.05 g、水合肼用量为2 mL、反应温度为80℃,脱溴效果较好,脱溴率达到98.5％.对催化剂重复使用进行了初步研究.对催化反应动力学进行了初步研究,结果表明,该多相催化反应是由表面反应速度控制,并符合一级动力学反应.对反应机理进行了初步探讨.     

MnOx/Al-SBA-15催化剂低温NH3选择性催化还原NO的原位红外研究简

用原位红外分别进行了MnO_x/Al-SBA-15催化剂上NH₃和NO+O₂的吸附态和瞬态实验以及NH₃+NO+O₂反应的稳态实验。结果表明,催化剂上存在着L酸位和B酸位,NH₃吸附在催化剂上形成配位态的NH₃和NH₄⁺,配位态的NH₃能脱氢形成—NH₂活性中间态。NO+O₂在催化剂上吸附形成硝酸盐类、硝基类和亚硝酸盐类。将NO+O₂通入预吸附NH₃的催化剂中时,表面的配位态的NH₃、NH₄⁺和—NH₂都会减少直至消失,SCR反应显著。而将NH₃通入预吸附NO+O₂的催化剂中时,只有硝基类和亚硝酸盐类减少,硝酸盐类基本不发生变化,SCR反应微弱。NH₃+NO+O₂稳态反应中,催化剂表面稳定存在着NH₄⁺和硝酸盐类,SCR反应显著。     

Cu-SBA-15催化湿式过氧化氢氧化水溶液中罗丹明B

采用水热晶化法合成了不同含铜量的Cu-SBA-15介孔分子筛,并且用XRD、N2吸附、TEM以及UV-vis对所合成的样品进行表征。以Cu-SBA-15为催化剂,H2O2为氧化剂,催化湿式过氧化水溶液中的罗丹明B,主要考察H2O2浓度、催化剂用量、处理温度、初始pH等因素对罗丹明B氧化效果的影响。结果表明,在同样的处理条件下罗丹明的脱色率明显高于TOC去除率,处理温度、初始pH对罗丹明B的脱色与氧化有重要影响。在罗丹明B初始浓度100 mg/L,H2O2初始浓度1.8 g/L,催化剂量0.3 g/L,温度60℃,pH为7.0,处理时间100 min时,罗丹明B的脱色率为98.6%,TOC去除率为62.8%。     

Ammonia volatilization losses and balance from urea applied to rice on a paddy soil

Ammonia volatilization loss and 15N balance were studied in a rice field at three different stages after urea application in Taihu Lake area with a micrometeorological technique. Factors such as climate and the NH4+-N concentration in the field floodwater affecting ammonia loss were also investigated. Results show that the ammonia loss by volatilization accounted for 18.6%-38.7% of urea applied at different stages, the greatest loss took place when urea was applied at the tillering stage, the smallest at the ear bearing stage, and the intermediate loss at the basal stage. The greatest loss took place within 7 d following the fertilizer application. Ammonia volatilization losses at three fertilization stages were significantly correlated with the ammonium concentration in the field floodwater after the fertilizer was applied. 15N balance experiment indicated that the use efficiency of urea by rice plants ranged between 24.4% and 28.1%. At the early stage of rice growth, the fertilizer nitrogen use efficiency was rather low, only about 12%. The total amount of nitrogen lost from different fertilization stages in the rice field was 44.1%-54.4%, and the ammonia volatilization loss was 25.4%-33.3%. Reducing ammonia loss is an important treatment for improving N use efficiency.     

南河底泥中微量镉的催化极谱测定

本文提出了一种新的碘化钾—苯并—15—冠—5—镉络合体系作基质,以极谱催化波测定痕量镉。峰电位在—0.8伏左右,检测限为2ppb,镉浓度与峰高在4—100ppb范围内呈线性关系。方法简单快速,且选择性好。镉浓度在7.5ppb,变异系数为2.6％,回收率为97.5—110％,用该法与常规AAS法对成都南河底泥中微量镉进行对比分析,获得了同样准确的结果。     

Transport and Immobilization of 2,4,6 15N-Trinitrotoluene in Soil Microcosms Subjected to Long Term Incubation Under Aerobic Conditions

¹⁵N-labeling and solid-state ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy was applied to study the immobilization of 2,4,6 trinitrotoluene (TNT) into soil organic matter (SOM). Uncontaminated soil from the Ap horizon of a Luvisol was mixed with ¹⁵N-TNT (enrichment: 99 atm%) and laid over an unspiked layer of the same material. The latter covered soil from the Bt horizon. The microcosms were aerobically incubated under laboratory conditions for up to 11 months. After 1 week, within the total microcosm approximately 90% of the added ¹⁵N (¹⁵N_add) were recovered, mostly in the top layer (87%). After 11 months, this amount decreased to 71%, indicating losses due to denitration or transamination. Within two months, half of ¹⁵N_add had been immobilized in the residues not extractable with organic solvents and water. The amount of the sequestered ¹⁵N_add remained fairly constant until the end of the experiment pointing towards a high stability of TNT-SOM associates. Solid-state ¹⁵N NMR revealed their formation by covalent binding, most tentatively as amides. Complete reduction of TNT to triaminotoluene (TAT) was not prerequisite. The most pronounced downwards movement of ¹⁵N-TNT occurred during the first two months. The major part of it, however, experienced quick immobilization, leaving approximately 10% of ¹⁵N_add recovered in the leachate at the end of the experiment. Calculations indicated contributions of inorganic ¹⁵N_add. Approximately 25% of its organic ¹⁵N_add originated from condensed N, suggesting that in soils the transport of partly reduced TNT is in close association with the organic matter of the soil solution to which they are covalently bound.     

SBA-15介孔分子筛处理废水中氨氮的研究

以具有较高比表面积及较大孔径的介孔分子筛SBA-15、Rod-SBA-15为载体,利用物理吸附的方法吸附废水中的氨氮,Rod-SBA-15由于具有较大的比表面积及孔径而具有较高的脱除效率,还通过测定不同分子筛用量、不同pH值及不同静置时间条件下的吸附效率来确定优选吸附条件,结果表明,分子筛用量优选3 mg/mL,pH值优选6～7,吸附时间优选20 min。     

Effects of heavy metals on the nitrogen metabolism of the aquatic moss Fontinalis antipyretica L. ex Hedw. A 15N tracer study

The assessment of pollution in aquatic systems necessitates an accurate indication of toxicity of heavy metals for organisms and ecosystems. We used the stable nitrogen isotope 15N to estimate the influence of the heavy metals Cd, Pb and Zn on the synthesis of nitrogen-containing fractions in the aquatic moss Fontinalis antipyretica. This method permits conclusions concerning inhibitory effects of these heavy metals on the assimilation of nitrogen and the biosynthesis of amino acids and proteins. The moss was exposed to metal concentrations of 25-500 microM over a period of 5-10 days. 15N abundance of exposed plants was compared with that of control plants. Similar to a loss of vitality determined using a fluorometric assay, a decrease of the 15N abundance in the N fractions of Fontinalis antipyretica was measured in dependence on the metal concentration. Nevertheless, the individual inhibition by the distinct metals was different, so that the following order of toxicity was derived: Cd > Pb > Zn.     

Comparison of maternal and fetal chromosome heteromorphisms to monitor maternal cell contamination in chorionic villus samples

Maternal cell contamination (MCC) presents a potential problem in the analysis of chorionic villus sampling (CVS) preparations for early prenatal diagnosis by chromosomal, biochemical and molecular methods. Through the comparison of fluorescent chromosome variants from CVS and maternal cells, we found three out of 50 samples to have MCC. One of these was observed on a direct preparation. Routine chromosome heteromorphism analysis suggested as a reliable method for monitoring MCC in CVS specimens.