涂覆在堇青石上的负载贵金属催化剂催化氧化甲醛的性能研究

将催化性能优异的负载贵金属催化剂与拟薄水铝石(Al OOH)溶胶混合,制备得到均匀的料浆,采用料浆涂覆法将其负载到堇青石蜂窝陶瓷基体上,考察了Al OOH含量对涂层形貌、负载量、涂层牢固度的影响,并对合成的整体式催化剂进行催化氧化甲醛性能测试。结果表明,合成的负载贵金属催化剂Pt粒子粒径为1.14nm时,可在17℃完全降解甲醛;涂覆过程中Al OOH含量越高,载体负载量越大,但过高易导致孔道堵塞,涂覆不均和涂层龟裂;超声振荡测试表明,Al OOH含量对涂层牢固度影响不大,当Al OOH含量为8(wt)%时,负载型蜂窝陶瓷的催化效果和涂覆效果最佳,可以在60℃下完全降解甲醛。     

H2O对Cu+/S2O82-/γ-Al2O3催化剂合成碳酸二甲酯性能的影响

反应温度120℃、压力3.0 MPa的条件下,考察了H₂O对浆态床DMC合成催化剂Cu⁺/S₂O₈^2-/γ-Al₂O₃活性的影响。结果表明,外界H₂O的引入加剧了催化剂的失活速率。对引入H₂O后回收催化剂进行了元素分析、XRD、DTG、Py-FT-IR和NH₃-TPD等表征,结果表明,H₂O的引入加速了催化剂中活性组分Cu的流失速率,生成更多没有催化甲醇氧化羰基化活性的Cu₂(OH)₃Cl晶体,加剧了催化剂的失活。     

自由能计算揭示苏氨酸对抗冻蛋白与冰晶结合能力的影响

采用分子动力学模拟和自由能计算研究了中等活性黑麦草抗冻蛋白(Lolium perenne antifreeze protein, LpAFP)冰结合位点(Ice-binding site, IBS)上苏氨酸(Thr)含量对其吸附冰晶能力的影响. 构建了一系列LpAFP突变体结构, 使其IBS上苏氨酸含量逐步增加, 其中包括一个对IBS上11个位点的突变, 使每个β片段均具有Thr-x-Thr基序(x是非保守的氨基酸, 主要是疏水氨基酸). 利用重要性采样算法(WTM-eABF)计算了LpAFP及其突变体与冰晶结合过程的自由能变化, 该算法结合了Well-tempering metadynamics的“填谷”和扩展拉格朗日自适应偏置力方法的“削峰”的优点, 显著提高了算法的采样效率. 结果表明, LpAFP突变体的IBS苏氨酸含量越高, 其与冰的结合在能量上越有利. 当突变体具有重复Thr-x-Thr基序时, 其与冰的结合能力最强. 进一步分析表明, 苏氨酸含量越高, IBS结合的液态水分子越多, 与冰晶结合时锚定包合水稳定存在的时间就越长, 抗冻蛋白的IBS与冰面之间的氢键网络也越稳定, 从而提高了抗冻蛋白与冰的结合能力. 增加苏氨酸残基的含量是提高中等活性抗冻蛋白抗冻活性的方法.     

煤的岩相显微组分对水煤浆性质的影响

通过对不同变质程度煤的岩相显微组分分析，考察了煤的岩相显微组分对水煤浆性质的影响。结果表明，在相近的灰分含量下，对于烟煤较高的镜质组、较低的丝质组含量有利于煤的成浆性和稳定性。从多元线性回归结果来看，镜质组和丝质组的含量对煤浆成浆性和流变性的影响较为明显，稳定组分的含量对水煤浆性质的影响较小。丝质组含量对稳定性作用明显，当煤中丝质组含量低于30%时，煤浆产生软沉淀的时间一般都在15d以上。煤的平均最大镜质组反射率与煤的成浆性具有较好的相关性，成浆性随煤的最大镜质组反射率增加而增加，因此可以用最大镜质组反射率来预测煤的成浆性。     

Solid-Phase Extraction with Slurry Injection of the Resin Into ETAAS for Trace Determination of Thallium in Natural Water

Thallium in natural water samples was determined by electrothermal atomic absorption spectrometry after 1000-fold enrichment by mini solid-phase extraction from a 100-mL sample solution. A Tl-pyrrolidine-1-carbodithioate complex formed in a sample solution of pH 1.6 was extracted on fine particles of a cellulose nitrate resin dispersed in the sample solution. The cellulose nitrate resin was then collected on a membrane filter (25mm^ø) by filtration under suction using a glass funnel with an effective filtration area of 0.64cm². As a result, a circular thin layer of the resin phase with a diameter of 9mm was obtained. Then the resin phase was carved out by an acrylate resin puncher with a 10-mm^ø hole to put it into a sample cup containing 100µL of 10mM HNO₃ containing 0.5mM NaCl. The resin phase was suspended in the solution by ultrasonication. 1000-fold enrichment was thus attained within 15min, and the suspension was delivered to electrothermal atomic absorption spectrometry. The linear calibration graph was obtained in the range of 0–4ng of Tl in 100mL of a sample solution. The detection limit obtained by 3 method was 0.19ng. The proposed method was applied to the determination of Tl in natural water samples. The results showed the concentration of Tl in seawater was 12.1±1.8pgmL^–1 for the calibration graph method and 12.6±1.4pgmL^–1 for the standard addition method. A snowmelt sample contained 20.7±1.0pgmL^–1 of Tl.     

改性污泥与无烟煤成浆性的研究

采用阴离子表面活性剂萘磺酸钠甲醛缩合物、聚羧酸钠作为分散剂,考察了不同污泥用量时污泥煤浆的成浆性能。结果表明,当污泥(干基)添加量为煤质量的4%时,成浆浓度超过60%,随着污泥用量的提高,污泥煤浆的成浆浓度降低。污泥加入后,浆体的稳定性增强,污泥比例越高,产生沉淀的时间延长。当污泥(干基)添加量为煤质量的4%时,产生沉淀的时间超过160h,与使用稳定剂效果相当。使用不同添加剂制备的污泥煤浆均呈假塑性。污泥疏松的絮状结构,蜂窝状的外表面,强大的吸水性是造成污泥煤浆成浆浓度下降,稳定性增加的主要原因。     

大庆催化油浆受热相分离行为的研究

借助于热台显微镜,对大庆油浆受热相分离行为进行了考察。通过在有氧、无氧条件及不同温度下对大庆油浆受热相分离行为的研究,并与之基本物性相互关联,从微观上探讨油浆的生成机理。实验表明,油浆中重组分含量高时,有氧条件下生焦就会加剧;同时高温短时间或是低温长时间下生焦倾向就会加大,而油浆的芳香性分布较宽条件下生焦可以得到减缓。     

Multisimplex Optimisation of the Purge-and-Trap Preconcentration of Volatile Fatty Acids, Phenols and Indoles in Cow Slurries

In this work the simultaneous purge-and-trap (P&;T) preconcentration of volatile fatty acids (acetic acid, propanoic acid, butanoic acid, iso-butanoic acid, pentanoic acid, iso-pentanoic acid, hexanoic acid and heptanoic acid), phenols (phenol, 4-methylphenol and 4-ethylphenol) and indoles (indole and 3-methylindole) from cow slurries was carried out in order to quantify them by gas chromatography flame ionisation detection (GC–FID). The optimisation of the preconcentration was performed using spiked cow slurries and the variables studied were the nature of the trap, the purge and heating time and the amount of inert salt (NaCl) added. Other parameters such as purge flow, sample volume, desorption time and temperature and baking time and temperature were kept constant. The first variable studied was the nature of the preconcentration trap. Four different commercially available traps (Vocarb 4000, Vocarb 3000, BTEXTRAP and Tenax/silica gel/carbon) were studied and Vocarb 3000 gave best results. Once the optimum trap was chosen, appearance of possible memory peaks were studied and significant signals were observed for 4-methylphenol, 4-ethylphenol, indole and 3-methylindole. In order to improve the blanks after each analysis the following actions were taken: (1) the needle sparger was located in the headspace of the sample and (2) all the replaceable parts of the P&;T (sample tube, needle sparger, Teflon ferrules, nuts, etc.) were washed, sonicated in acetone for 15 min and dried in an oven at 350 °C. Once the blank problems were minimised, the remaining variables (purge and heating time and the amount of NaCl) were optimised using the MultiSimplex^® program, which enabled the study of several variables and responses simultaneously. Optimum conditions for the simultaneous preconcentration were obtained after 24 experiments and the final optimised preconcentration conditions were as follows: 0.4 g of NaCl were added to 10 mL sample which was heated at 80 °C for 10 min and purged for 20 min while the Vocarb 3000 trap remained at room temperature. Once the purge step was over, the trap was desorbed at 250 °C for 6 min and baked at 260 °C for 10 min. After the optimisation of the P&;T based preconcentration, the precision (within and among days), accuracy and detection limits of the method were studied.     

结冰过程对溶解性有机质典型组分还原Cr(Ⅵ)的影响

研究了结冰过程对溶解性有机质(DOM)的4种典型组分草酸、酒石酸、苹果酸和柠檬酸还原Cr(Ⅵ)的影响.结果表明,在低浓度下Cr(Ⅵ)在水溶液中不能被4种有机酸所还原;而在冰中,不同的有机酸对Cr(Ⅵ)的去除均有促进作用,且去除效果随着有机酸浓度的增大逐渐增强.4种有机酸的作用效果强弱顺序为草酸酒石酸苹果酸柠檬酸.通过使用不同浓度的无机盐和无机酸可以改变冰表面上类似液体层的厚度来抑制Cr(Ⅵ)的还原,作用效果与无机盐种类无关.溶液的初始pH值和有机酸结构是影响Cr(Ⅵ)还原的重要因素.实验条件下冷冻浓缩效应的富集倍数至少可达10~3,对冰中草酸去除Cr(Ⅵ)有明显的促进作用.     

Ordered porous TiO2 films obtained by freezing and the application in dye sensitized solar cells

TiO₂ films with ordered porous structure were prepared by freezing. By simply freezing wet TiO₂ film on a cold copper plate, ice crystals could grow from bottom of film. Removing such ice crystals then led to ordered, micro-sized pores in the films. With assistance of scanning electron microscopy and N₂ adsorption–desorption isotherms, micro-structural properties of the films were studied. Coarsening behavior of ice crystals was analyzed based on evolvement of the micro-structure. It was found that, both larger film thickness and longer freezing time were beneficial for the formation of ordered porous structure, which was caused by enhanced ice crystals growth. The films were then used to fabricate photoanode of dye sensitized solar cells, of which the photo-to-electric power conversion efficiency was evaluated. It was observed that, solar cell made of ordered porous TiO₂ film came out with 13% larger photo-current density comparing to that made of conventional doctor blading method, which is due to the enhanced light scattering by the ordered porous structure.