气相色谱法检测大气中N2O浓度

由于受大气中Ｏ２、Ｈ２Ｏ和氯氟烃的干扰，大气中的Ｎ２Ｏ难于用简单的气相色谱法连续观测。实验中对带有电子捕获检测器的气相色谱仪（Ｇ－ＥＣＤ）进行了改进，系统中安装了１０通进样反吹阀和４通切换阀，色谱系统中同时采用两根ＰｏｒａＰａｋＱ填充柱，并在进样系统中安装了水蒸汽和ＣＯ２过滤吸收器。这样，干扰物不进入检测器，对Ｎ２Ｏ信号没有干扰，从而提高了Ｎ２Ｏ分析灵敏度和精确度。从１９９２年１１月起，我们开始对北京大气Ｎ２Ｏ浓度进行长期定位测检。用这种方法测得的北京大气Ｎ２Ｏ月平均浓度介于３０１±９．８ｐｐｂｖ至３３５±２２．５ｐｐｂｖ之间，平均值为３１７±１２．８ｐｐｂｖ。     

用于负压下气体分析的气相色谱仪的研制

介绍一种可同时分析负压样品中常量Ｏ２,Ｎ２,ＣＯ和微量ＣＯ２的自制专用气相色谱仪。仪器在 负压下取样,经活塞升压后进样。在流程中样品气同时进入并列的色谱柱,再分别检测。常量组分使用热导池检测,微量组分使用氦离子化检测器检测。ＣＯ２的检测灵敏度为１０＾－６量级。实验表明,仪器结构简单,操作方便稳定性好,适合于负压气样的在线分析,负压气样中全组分的分析方法具有推广价值。     

毛细管多维气相色谱法分析炼厂气

用ＨＰ６８９０气相色谱仪,使用多孔层空心毛细管柱（ＰＬＯＴ）,选用ＨＰ－ＰＬＯＴ／Ｐｏｒａｐａｃｋ Ｑ色谱柱测定ＣＯ２;ＨＰ－ＰＬＯＴ ５Ａ分子筛柱测定Ｏ２,Ｎ２,ＣＨ４;ＨＰ－ＰＬＯＴ／Ａｌ２Ｏ３柱测定有机烃类。采用３阀４柱色谱运行系统,用ＦＩＤ及ＴＣＤ分别检测烃类及无机气体组分。用色谱工作站控制气动切换阀切换气样走向及两种检测器数据的转换校正和归一化定量计算,用已知物对照法定性,测定了炼厂气中     

不同阳离子Y分子筛上金属络合物吸附和分解Ⅱ.Co(CO)3NO吸附和分解和红外光谱表征

采用红外光谱表征了含不同阳离子的Ｙ分子筛上Ｃｏ（ＣＯ）３ＮＯ的吸附和分解及其和阳离子的作用。结果表明，Ｃｏ（ＣＯ）３ＮＯ吸附后主要形成Ｃｏ（ＣＯ）ｘＮＯ（ｘ＝２，３），并出现热稳定性较高的Ｃｏ（ＮＯ）２＾２＋。产生Ｃｏ（ＮＯ）２＾２＋的机制和最终分解产物与分子筛阳离子的性质有关。ＮａＹ上Ｃｏ（ＮＯ）ｘＮＯ歧化产生少量Ｃｏ（ＮＯ）２＾２＋，分解产物主要为Ｃｏ（０）；ＣｏＹ中Ｃｏ＾２＋的存在部分避免了     

不同阳离子Y分子筛上金属络合物的吸附和分解 Ⅱ.Co(CO)_3NO吸附和分解的红外光谱表征

采用红外光谱表征了含不同阳离子的Ｙ分子筛上Ｃｏ（ＣＯ）３ＮＯ的吸附和分解及其和阳离子的作用．结果表明，Ｃｏ（ＣＯ）３ＮＯ吸附后主要形成Ｃｏ（ＣＯ）ｘＮＯ（ｘ＝２，３），并出现热稳定性较高的Ｃｏ（ＮＯ）２＋２．产生Ｃｏ（ＮＯ）２＋２的机制和最终分解产物与分子筛阳离子的性质有关．ＮａＹ上Ｃｏ（ＣＯ）ｘＮＯ歧化产生少量Ｃｏ（ＮＯ）２＋２，分解产物主要为Ｃｏ（０）；ＣｏＹ中Ｃｏ２＋的存在部分避免了Ｃｏ（ＣＯ）ｘＮＯ的歧化，分解得到的Ｃｏ（０）含量较高；ＮｉＹ，尤其ＣｕＹ阳离子和吸附物种发生电子转移，形成ＮＯ＋中间物种，氧化Ｃｏ（０）产生Ｃｏ（ＮＯ）２＋２，分解产物为Ｃｏ（０）和Ｃｏ（Ⅱ）的混合物．     

[Cu2（Gly—GlyO）2（4,4‘—bpy）（OH）2].9H2O配合物的合成,晶…

将Ｇｌｙ－ＧｌｙＯ，４，４＇－联吡啶与Ｃｕ（ＮＯ３）２．Ｈ２Ｏ在二次水溶液中反应，合成出以４，４＇－ｂｐｙ为中继基，Ｃｌｙ－ＧｌｙＯ为螯环的新型双核铜配合物，经Ｘ射线单晶结构分析确定该配合物晶体的化学结构式为［（Ｈ２ＮＣＨ２ＣＯＮＨＣＨ２ＣＯＯ）Ｃｕ（ＯＨ）（Ｃ１０Ｈ８Ｎ２）Ｃｕ（ＯＨ）（Ｈ２ＮＣＨ２ＣＯＮＨＣＨ２ＣＯＯ）］．９Ｈ２Ｏ。晶体属Ｐ１空间群，晶胞参数α＝１．１４１２ｎｍ，ｂ＝１．２２９     

多维气相色谱法测定催化裂化气体组成

１引言 催化裂化气体组成测定是炼油厂中重要的分析项目之一,其组成除含有Ｃ１～Ｃ５等轻烃组分外,还含有Ｈ２、Ｏ２、Ｎ２、ＣＯ、ＣＯ２等永久性气体,常规方法是利用３台气相色谱仪,一个样品３次进样,达到全组分分离,操作繁琐且准确度差。本文介绍的多维气相色谱法测定催化裂化气体组成,一个样品只需一次进样就能达到全组分的分离检测,操作简便,且重复性好,准确度高。２实验部分２．１仪器和色谱柱 ＨＰ５８９０Ⅱ型气相色谱仪;ＨＰ３３９６Ⅱ型积分仪（美国惠普公司）。癸二腈（柱１Ａ０．６ｍ×３．２ｍｍｉ．ｄ．：柱１Ｂ …     

以活性碳纤维为载体的催化剂对NO的催化还原作用 三、铜-钴复合催化剂

采用多种催化剂组份复合往往可以弥补单一组份催化剂存在的某些不足之处。本工作在铜系和镍系ＡＣＦ催化剂研究的基础上，进一步研究了铜－钴复合型ＡＣＦ催化剂对ＮＯ的催化还原作用，系统研究了复合催化剂的制备方法、反应条件等对催化剂活性的影响，并采用各种仪器分析方法研究复合型催化剂的结构以及与催化活性的关系。实验结果表明，Ｃｕ（ＮＯ３）２－Ｃｏ（ＮＯ３）２－ＡＣＦ复合催化剂两种组份有协同效应，它比单组份催化剂不仅具有更高的催化还原ＮＯ活性，ＮＯ转化率可高达９４％，而且温度适应范围广，催化剂寿命长。以５０：５０（Ｃｕ（ＮＯ３）２：Ｃｏ（ＮＯ３）２）混合溶液浸渍后热处理获得的催化剂具有最佳的催化效果。催化剂活性组份主要为单质铜和Ｃｏ。并观察了催化剂负载量、催化剂用量、载气流量、ＮＯ及ＮＨ３流量等对ＮＯ转化率有影响。     

聚N,N-双水杨醛乙二胺合钴修饰超微电极的制备及其在一氧化氮测定中应用的研究

通过电化学聚合法制备了聚Ｎ，Ｎ－双水杨醛乙二胺合钴［ｐｏｌｙＣｏ（Ｓａｌｅｎ）］修饰超微电极，研究了该修饰电极的电催化性质及其在一氧化氮（ＮＯ）测定中的应用．实验结果表明，ｐｏｌｙＣｏ（Ｓａｌｅｎ）修饰超微电极对ＮＯ的测定有高的灵敏度，ＮＯ的浓度在２．０×１０－８～２．８×１０－６ｍｏｌ／Ｌ范围内，电流与浓度呈良好的线性关系，线性相关系数为０．９９９８，检出限为１．０×１０－８ｍｏｌ／Ｌ；该电极进一步修饰Ｎａｆｉｏｎ后，生物体中常见的物质如抗坏血酸、儿茶酚胺类神经递质的代谢物、ＮＯ的氧化产物ＮＯ－２等不干扰测定．本传感器可以满足ＮＯ在体分析的需要．     

天然气和氧偶联制环氧乙烷催化剂的反应性能

研制了天然气和氧经偶联反应制环氧乙烷的Ａｇ－Ｂａ－Ｃｓ／Ａｌ２Ｏ３催化剂（ＮＥＯ－１）。用Ｎ２＋Ｏ２＋Ｃ２Ｈ４和偶联产物气加氧作原料气，在２５０℃，空速２５００ｈ＾－１时，乙烯转化率和ＥＯ选择性分别达到了３０％和８０％，ＮＥＯ－１催化具有适宜的比表面和孔结构，用ＸＰＳ分析发现，与新鲜的催化相比，经活化和反应后的催化剂表面的Ｂａ，Ｃｓ原子浓度增高，并具有较多的吸附氧物种。     

A fully automatic system for underway N2O measurements based on cavity ring-down spectroscopy

N₂O is one of the most important greenhouse and ozone-depleting gases and has been the source of considerable concern in recent years. The oceans account for ~ 1/4 of the global N₂O emission budget; however, the oceanic N₂O source/sink characteristics are not well understood. To enhance the study of oceanic N₂O source/sink characteristics, our laboratory developed a fully automatic underway system for surface water N₂O concentration and atmospheric N₂O mole fraction measurements consisting of a cavity ring-down spectroscopy (CRDS) instrument and an upstream device. The developed device can be programmed to switch the CRDS measurements from the equilibrator headspace to the atmospheric sample and the reference gas sample. The surface water N₂O concentration is calculated from the equilibrium headspace N₂O mole fraction in the equilibrator. The response time of this equilibrator is ~ 3.4 min, and the estimated precision of this method for surface water N₂O measurements is better than 0.5% (relative standard deviation, RSD), which is one order of magnitude better than that of traditional gas chromatographic methods and can be further optimised. Data are acquired every 20 s, and the calibration frequency requirement of this system is approximately 7–10 days. This labor-saving underway system is a powerful tool for high-precision and high-resolution measurements of atmospheric and oceanic N₂O and can significantly improve the study of the characteristics of oceanic N₂O sources/sinks and their response to climate change.     

A system for the automated static headspace analysis of dissolved N2O in seawater

A new automated static headspace N₂O analysis technique has been developed that includes a CTC autosampler composed of agitator and headspace modules, a combined-valve switching system and ECD Gas Chromatography. This new CTC autosampling technique is more efficient for sample analysis than similar systems and takes approximately 10 mins to analyze each sample without pre-equilibration. The accuracy and precision of this method are approximately 2% each. Laboratory and field results demonstrate that this technique is suitable for seawater sample analysis.     

Study of NOx and CO2 production of cultivated soil in closed microcosm experimental system

The aim of present project was to develop a microcosm experimental method for estimation of NO_x and CO₂ emission of microbial origin from cultivated soil. The effect of different factors (such as temperature, water supply, mineral-N source and organic matter addition, role of soil organisms and heavy metal contamination) that controlling the accumulation of N₂O and CO₂ in soil atmosphere and release to air was studied in closed microcosm laboratory model experiments. The headspace gas composition of closed glass vessels of 800-1200 cm³ containing 100-200 g brown forest soil sample was analysed. The N₂O and CO₂ concentration of gas samples was analysed by gas chromatographic methods and NO-content by means of chemiluminescent detection. Concerning the results, it can be stated that the applied microcosm experimental model proved to be a suitable tool for detecting the effect of factors influencing the NO_x and CO₂ release from agricultural soil. The temporal changes of N₂O and CO₂ concentration demonstrated the impact of the coupled microbial processes resulting in these greenhouse gases. The gas production depended on the soil moisture level, temperature and C/N ratio significantly. The inhibitory effect of toxic heavy metals (e.g. Cd) could also be affected by the C/N ratio. The appearance of NO as an intermediate of microbial processes was observed as well.     

Co取代的六铁酸盐在N2O催化分解反应中的应用

采用溶胶-凝胶法制备了Co取代的Ba₂Mg_2-xCo_xFe₁₂O₂₂(x=0.0~2.0)催化剂,并考察了其在高浓度N₂O(30vol%)分解反应中的催化活性.结果表明,Co的取代显著提高了Ba₂Mg₂Fe₁₂O₂₂催化剂活性,当x=2时,N₂O的完全分解温度从1123K降至973K;提高催化剂焙烧温度会导致其表面积降低,进而降低其催化活性;但采用微波加热则能显著提高催化剂活性.     

氮肥管理对夏玉米土壤CH4和N2O排放的影响

通过设置四个不同的氮肥管理措施, 即氮肥施用量300 kg N/ha (N300)和250 kg N/ha (N250)、改进的施肥模式(Optimized)以及施用缓释肥(SRU), 研究华北平原夏玉米生长季土壤与大气之间CH₄和N₂O的交换通量及相应措施的减排潜力. 结果表明, 在2008年整个夏玉米生长季, 土壤都是大气CH₄的净吸收库和N₂O的排放源. 夏玉米生长季土壤氧化吸收的CH₄总量从大到小依次为Optimized > N250 > SRU > N300, 对应的吸收总量依次为624.16、590.07、487.89以及316.02 g CH₄-C/ha, 各处理间氧化吸收的CH₄总量无显著差异. 与N300和N250这两个处理相比, 依据夏玉米对氮肥的需肥规律以及玉米根层土壤速效氮的供给能力而确定氮肥施用量, 同时再平衡施用磷肥和钾肥的改进施肥模式能够显著降低夏玉米生长季N₂O的排放. 施用聚乙烯包膜的尿素也能够显著降低夏玉米季N₂O的排放. 夏玉米生长季土壤排放的N₂O总量从大到小依次为N300 > N250 > Optimized > SRU, 对应的排放总量依次为3462.18、2340.07、1680.00以及911.91 g N2O-N/ha, 相应的N₂O排放系数分别为1.15%、0.94%、0.91%以及0.30%.     

Cu2O/g-C3N4催化合成吲哚-2-羧酸酯

我们通过原位还原的方法将吸附在g-C3N4表面上Cu2+还原,制备出Cu2O/g-C3N4复合材料,并利用XRD、SEM、FT-IR、XPS等分析手段表征Cu2O/g-C3N4.表征结果显示:Cu元素主要以Cu2O的形式吸附在g-C3N4载体上.另外,还考察了Cu2O/g-C3 N4在“一锅法”合成吲哚-2-甲酸乙酯的反应中的催化性能.结果表明:即使在较低的催化担载量和温和的反应条件下,Cu2O/g-C3 N4仍能表现出良好的催化性能并获得44.1％的收率.     

Methane and nitrous oxide concentration and emission flux of Yangtze Delta plain river net

Methane (CH4) and nitrous oxide (N2O) saturation concentration and gas-water interface emission flux in surface water of the Yangtze Delta plain river net were investigated in summer at representative sites including the upper reaches of the Huangpu River and the rivers in the Chongming Island. The results show that the CH4 concentration in river water ranged from 0.30±0.03 to 6.66±0.14 μmol.L-1, and N2O concentration ranged from 13.8±2.33 to 435±116 nmol.L-1. River surface water had a very high satura- tio...     

FFT analysis of atmospheric trace concentration of N2O continuously monitored by gas chromatography and cross-correlation to climate parameters

To investigate the characteristics of N₂O concentration, we applied several types of time series analyses such as fast Fourier transform (FFT), auto-correlation, and cross-correlation, to 2.5-year time series data of trace N₂O concentration continuously monitored by gas chromatography and meteorological data, measured in an urban area of Nagoya. It was found that there is a positive correlation between atmospheric N₂O concentration (ppbv) and, both steam pressure (hPa) and temperature (°C). In addition, negative and positive correlations in atmospheric pressure and in solar flux were also found, respectively. These findings suggest an enrichment of N₂O through environmental steam during the summer season, particularly in urban areas. On the other hand, the correlation to wind direction shows a variation with amplitude of 7 ppbv, from the north-west to the south-east, and a seasonal variation up to 12 ppbv, from winter to summer. These results support the hypothesis that atmospheric steam controls the N₂O concentration in urban areas. In addition, the correlation with wind direction suggests the existence of an emission source in the direction of seaside areas.     

Activation of Pd-Ag Catalyst for Selective Hydrogenation of Acetylene via Nitrous Oxide Addition

Hydrogenation of acetylene in the presence of a large excess of ethylene has been investigated on the Pd-Ag catalyst under 60°C and a space velocity of 2,000 h^–1. It was found that an enhancement in the performance of Pd-Ag catalyst can be obtained by pretreatment with N₂O. It is suggested that added N₂O on the catalyst before use not only augments the sites associated with ethylene production from acetylene but also depletes the sites responsible for direct ethane formation.