Palladium-citric acid-ammonium fluoride as a matrix modifier for overcoming of interferences occurring during the direct determination of Sn in aqua regia extracts from environmental samples by D2-ETAAS

When tin is to be determined in such a complex matrix like aqua regia extracts of environmental samples by electrothermal atomic absorption spectrometry (ETAAS), spectral interferences occur when deuterium-lamp (D₂) background correction is used, even using high pyrolysis temperature of 1400 °C achieved with palladium with citric acid chemical modifier. We have found that the further addition of NH₄F to palladium with citric acid chemical modifier is essential for overcoming the above-mentioned problems for which aluminium oxide is most probably responsible. It is supposed, that NH₄F enables volatilization of the alumina matrix formed by hydrolysis from the chloride salt and interfering in a gas phase via the formation of AlF₃ which could be, in contrast to aluminium oxide, removed from the graphite furnace during the pyrolysis stage. Using the proposed chemical modifier, the direct and accurate determination of Sn in aqua regia extracts from rocks, soils and sediments is possible even when using matrix free standard solutions. This presumption was confirmed by the analysis of certified reference samples and by the comparison with inductively coupled plasma time of flight mass spectrometry (ICP-TOFMS) method. Characteristic mass and LOD value for the original sample (10-μL aliquots of sample) was 17 pg and 0.055 μg g⁻¹, respectively.     

可瓷化硅橡胶材料的研究

研究了一种可瓷化硅橡胶,其特点是在火灾发生时可在金属线外形成瓷化绝缘保护层,600℃的成瓷温度大幅度低于目前文献报道的成瓷温度。实验得到的优化瓷化填料配方为:相对于100份混炼胶,氧化铝10份、硅灰石15份、结构控制剂9份、碳酸锂3份。在此配方条件下,未瓷化硅橡胶的断裂伸长率316%、拉伸强度10.79MPa、体积电阻率134×10~(12)Ω·cm,其在600℃、800℃瓷化后的抗压强度分别为3.47MPa、10.13MPa、体积电阻率≥28×10~(12)Ω·cm,满足电缆用硅橡胶的力学和绝缘要求。经热重分析及SEM分析可知加入瓷化填料后,试样烧蚀重量减少了39.4%,烧蚀残留率大大提高,且成瓷试样结构致密。     

Morphology-controlled electrochemical sensing amaranth at nanomolar levels using alumina

Different-shaped aluminas were readily prepared via hydrothermal reaction. It was found that the morphology and the electrochemical sensing properties of alumina were heavily dependent on the reaction time. When extending the reaction time from 6 h to 24 h, the obtained alumina samples changed from amorphous bumps to regular microfibers in diameter of 200 nm, as confirmed by scanning electron microscopy. Transmission electron microscopy observation revealed that longer reaction time was beneficial for the formation of porous and uniform fiber-like structures. Electrochemical tests proved that alumina microfibers were more active for the oxidation of amaranth and exhibited much higher enhancement effect, compared with alumina bumps. On the surface of alumina microfibers, the oxidation peak currents of amaranth increased remarkably. The influences of pH value, amount of alumina microfibers, and accumulation time on the signal enhancement of amaranth were discussed. As a result, a novel electrochemical method was developed for the detection of amaranth. The linear range was from 1 to 150 nM, and the detection limit was 0.75 nM after 1-min accumulation. The analytical application in drink samples was investigated, and the results consisted with the values that obtained by high-performance liquid chromatography.     

硝化甘油在α-Al_2O_3(0001)和γ-Al_2O_3(110)表面吸附的理论计算

选取硝化甘油(NG)和氧化铝(Al_2O_3)分别作为推进剂中的含能增塑剂和燃料表面的模型,研究了含硝酸酯类增塑剂与推进剂中燃烧剂表面的微观作用机理.采用基于密度泛函理论的第一性原理方法和全电子双数值基组研究了NG在α-Al_2O_3(0001)和γ-Al_2O_3(110)表面的吸附作用.计算结果表明,NG可以在α-Al_2O_3(0001)和γ-Al_2O_3(110)表面发生强烈化学吸附;吸附导致相应的O—NO_2键被明显拉长并断裂,无能垒自发产生NO_2自由基,该解离过程放出大量的热,吸附能高达约175.7 kJ/mol;NG在完全羟基化的α-Al_2O_3(0001)和γ-Al_2O_3(110)表面上的吸附明显减弱,从强烈的化学吸附转变成以氢键作用为主的物理吸附,吸附能只有约50.0 kJ/mol;而在部分羟基化的α-Al_2O_3(0001)和γ-Al_2O_3(110)表面上可以同时发生物理吸附和化学吸附,且两种机制并不存在明显的协同或催化作用.     

Ethylene Glycol as New Mobile Phase for Resolution of Two-Component Mixture of Cationic Surfactants on Alumina Surface

Aqueous ethylene glycol (ethane 1,2 diol) as a green mobile phase has been used for thin layer chromatographic (TLC) studies of cationic surfactants on alumina layers. Nineteen solvent systems were used to examine the mobility of the surfactants and to discover the best TLC system for the selective separation of dodecyl trimethylammonium bromide (DTAB) from multi-component mixture of other surfactants. Among the TLC systems studied, M₃ (ethylene glycol: water, 8:2) was best for achieving the selective separation of DTAB from multi-component mixture of other surfactants because in this mobile phase mobility of all surfactants except DTAB were insignificant. Effect of organic additives in aqueous ethylene glycol mobile phase on the mobility of surfactants was examined. The results obtained on laboratory made alumina TLC plates and commercially available precoated alumina HPTLC plates were compared. The lower limits of detection of DTAB, CPC, CTAB, HDTAC, and TTAB were 0.02, 0.05, 0.04, 0.06, or 0.08 µg per zone respectively. The resolution of mixture of cationic surfactants was also examined in the presence metal cations as an impurity in the analyzed sample.     

复合软模板法可控制备红毛丹状AlOOH/Al2O3纳米材料

以Al(NO₃)₃为铝源,尿素为均相沉淀剂, 在聚乙二醇400(PEG4000)-DL-天冬氨酸形成的复合软模板体系中, 通过简单的常压回流方式成功合成出形貌和尺寸较为均一的红毛丹状γ-AlOOH纳米结构, 继而考察了反应物和添加剂用量对前驱体形貌和尺寸的影响, 并对γ-AlOOH纳米结构可能的形成机理进行了探讨. 实验结果表明, 所合成的红毛丹状γ-AlOOH具有球中球的核壳结构, 统计得内球直径约为400 nm, 外壳外径约为600 nm, 密集状态的壳层厚度约为15 nm, 毛刺状凸出物长度可达60 nm以上. 前驱体样品经600℃煅烧5 h后即转变为具有良好形貌继承性的γ-Al₂O₃, Brunauer-Emmett-Teller (BET) N₂-吸附实验表明其比表面积高达299.97 m²·g^-1.     

制备方法对Al2O3掺杂Pt/WO3-ZrO2催化剂上正庚烷异构化反应的影响

采用恒pH法和非恒pH法制备了Al₂O₃掺杂的Pt/WO₃/ZrO₂催化剂,并用N₂吸附-脱附、X射线衍射、紫外-可见漫反射、CO化学吸附、X射线光电子能谱、²⁷Al魔角旋转核磁共振和吡啶吸附红外等技术对催化剂进行了表征.结果表明,相比于非恒pH法制备的催化剂,恒pH法制备的催化剂具有较高的比表面积和Pt分散度,在H₂气氛中产生更多的B酸位,从而表现出更高的催化正庚烷临氢异构化反应活性; 在200℃和质量空速0.9h^-1的反应条件下,正庚烷转化率达70.0%,明显高于非恒pH法制备的催化剂(43.5%).     

Dispersion of Colloidal Alumina using a Rhamnolipid Biosurfactant

Dispersability of colloidal alumina in water has been studied using a rhamnolipid containing biosurfactant. Zeta potential measurements revealed that the surface charge of alumina was altered due to adsorption of the biosurfactant and the iso‐electric‐point of alumina shifted from pH 9 to 6.3. Sedimentation tests indicated that the alumina suspension was completely dispersed for 3–5 hours in the presence of biosurfactant after which some settling was observed. Stability of the suspension in the time period studied was found to be independent of pH. Capillary suction time measurements showed that the alumina suspension was dispersed in the presence of the biosurfactant and varied with pH. Maximum dispersion is obtained in the pH range of 3.5–5 and 7–11 while a minimum is obtained around pH 6. This behavior is consistent with the changes in zeta potential in the presence of the biosurfactant and thus capillary suction time measurements appeared to be more reliable than the sedimentation tests. Optimization studies showed that about 60 mg/g of biosurfactant was necessary for best dispersion and dispersion could be done up to 40% solids. The application of a natural biosurfactant for dispersing colloidal alumina has been demonstrated.     

Ni基催化剂催化燃油重整耦合选择性催化还原NOx反应

分别以La₂O₂CO₃, CeO₂, ZrO₂和Al₂O₃为载体, 采用浸渍法制备了Ni基重整催化剂, 并以正十二烷模拟车载燃油进行催化重整反应以同时制备小分子碳氢化合物(HCs)和H₂, 考察了其在4wt%Ag/Al₂O₃上选择性催化还原(HC-SCR)氮氧化物(NO_x)的性能. 采用N₂吸附-脱附、X射线粉末衍射、H₂程序升温还原和热重等手段对Ni基催化剂进行了表征. 结果表明, 随着重整催化剂氧化还原性能增强, 产物中H₂浓度增加, 可参与SCR反应的HCs含量减少, 从而导致重整-SCR耦合体系上NO_x净化活性温度窗口向低温移动, NO_x最高转化率降低. Ni/ZrO₂+Ag/Al₂O₃耦合体系中H₂/HCs符合SCR反应所需的最优比例, 在柴油车典型排气温度范围内表现出良好的NO_x净化能力. 同时, 在Ni/ZrO₂+Ag/Al₂O₃耦合体系上考察了其燃油重整-SCR的活性稳定性. 结果显示, 重整催化剂的耐久性有待进一步提高.     

Pt–Al2O3 nanocoatings for high temperature concentrated solar thermal power applications

Nano-phased structures based on metal–dielectric composites, also called cermets (ceramic–metal), are considered among the most effective spectral selective solar absorbers. For high temperature applications (stable up to 650 °C) noble metal nanoparticles and refractory oxide host matrices are ideal as per their high temperature chemical inertness and stability: Pt/Al₂O₃ cermet nano-composites are a representative family. This contribution reports on the optical properties of Pt/Al₂O₃ cermet nano-composites deposited in a multilayered tandem structure. The radio-frequency sputtering optimized Pt/Al₂O₃ solar absorbers consist of stainless steel substrate/ Mo coating layer/ Pt–Al₂O₃/ protective Al₂O₃ layer and stainless steel substrate/ Mo coating layer /Pt–Al₂O₃ for different composition and thickness of the Pt–Al₂O₃ cermet coatings. The microstructure, morphology, theoretical modeling and optical properties of the coatings were analyzed by the x-ray diffraction, atomic force, microscopy, effective medium approximation and UV–vis specular and diffuse reflectance.