In situ Remediation of Petroleum Contaminated Groundwater by Permeable Reactive Barrier with Hydrothermal Palygorskite as Medium

The permeable reactive barrier(PRB) has proven to be a cost-effective technique to remediate the petroleum contaminated groundwater at a northeast field site in China. In this study, the geology, hydrogeology and contamination characterization of the field site were investigated and the natural hydrothermal palygorskite was chosen as a reactive medium. Furthermore, the adsorption of the total petroleum hydrocarbons(TPH) in the groundwater onto hydrothermal palygorskite and the adsorption kinetics were investigated. The results indicate that the removal rates of TPH, benzene, naphthalene and phenantharene could all reach up to 90% by hydrothermal palygorskite with a diameter of 0.25―2.00 mm that had been thermally pretreated at 140 ℃. The adsorption of TPH onto hydrothermal palygorskite after pretreatment followed a pseudo-second-order kinetic model and a Langmuir adsorption isotherm, suggesting that the theoretic adsorption capacity of hydrothermal palygorskite for adsorbate could be 4.2 g/g. Scanning electron microscopy(SEM), infrared spectroscopy(IR), X-ray diffraction(XRD) and X-ray fluorescence spectroscopy(XRF) were carried out to analyze the adsorption mechanism. The results reveal that hydrothermal palygorskite is a fibrous silicate mineral enriched in Mg and Al with large surface area and porosity. The dense cluster acicular and fibrous crystal of hydrothermal palygorskite, and its effect polar group ―OH played an important role in the physical and chemical adsorption processes of it for contaminants. This study has demonstrated hydrothermal palygorskite is a reliable reactive medium for in situ remediation of petroleum contaminated groundwater at field sites.     

聚丙烯酸对自然水体生物膜吸附镉的影响

选择聚丙烯酸(PAA)为水中溶解态高分子天然有机质的代表, 研究了PAA对自然水体生物膜吸附重金属Cd的影响, 包括不同浓度的PAA对吸附的影响, PAA对特定pH下吸附等温线的影响以及不同pH下按不同顺序添加PAA时对吸附的影响. 研究结果表明, PAA的存在一般会降低生物膜对Cd的吸附, 其影响程度与PAA的浓度、 溶液pH、 吸附顺序及生物膜厚度等有关. PAA与Cd的浓度比越高, 其对吸附的影响越显著. 吸附溶液pH越高, PAA的影响越显著. 吸附顺序对吸附的影响在pH较低时不明显, 当pH较高时, 先加PAA后加Cd及两者同时吸附时对吸附的降低作用接近且较大, 先加Cd后加PAA时对吸附的降低作用相对较小. 生物膜较薄时PAA的影响更显著. PAA对生物膜吸附Cd的影响主要由PAA与生物膜之间对Cd的竞争以及三元表面配合物的生成与吸附2种因素共同决定. 高pH会促进PAA与Cd的配合而不利于带负电的配合物在生物膜上的吸附.     

碳纳米管和碳纳米管-四氢呋喃水合物的储氢特性

研究了单壁碳纳米管(SWNTs)干法储氢和碳纳米管(SWNTs)-四氢呋喃(THF)水合物法储氢的过程. 结果表明, 实验所用的SWNTs在16.5 MPa压力下, 温度为0.5 ℃时, 氢气的吸附存储量为0.75%(质量分数), 经浓酸处理后, 氢气的存储量可以达到1.15%, SWNTs-THF水合物法储氢量为0.37%, 与碳纳米管干法储氢相比, 储氢量有所降低.     

β-环糊精功能化聚丙烯腈纳米纤维的制备及对亚甲基蓝的吸附性能β-环糊精功能化聚丙烯腈纳米纤维的制备及对亚甲基蓝的吸附性能

以N,N-二甲基甲酰胺(DMF)为溶剂, 利用静电纺丝法制备了聚丙烯腈(PAN)/β-环糊精(β-CD)纳米纤维. 通过场发射扫描电镜、红外光谱和粉末XRD对纳米纤维进行了表征, 并检测了纺丝溶液的电导率和黏度. 结果表明, β-CD的添加量可以改善纳米纤维的形貌, 固定在纤维上的β-CD保留了空腔结构, 为其在纳米纤维中发挥超分子特性提供了可能. 通过紫外-可见光谱法研究了PAN/β-CD纤维对亚甲基蓝(MB)溶液的吸附性能. 结果表明, 纳米纤维中的β-CD显著提高了PAN/β-CD纤维对MB的吸附能力, 使其在吸附分离、电化学传感器及药物控制释放等领域具有潜在的应用价值.     

梳型聚合物在固液界面吸附形态的Monte Carlo模拟

采用Monte Carlo模拟方法对PAA/PEO梳型聚合物在固液界面吸附形态进行了模拟,得到了聚合物在液相中聚集形态以及在固液界面上吸附形态的瞬时构型,同时获得了聚合物的吸附层厚度、均方回转半径和吸附在固液界面的各种链段数等微观信息. 结果证实：随着聚合物的接枝数Np增大,聚合物在液相中的扩散系数逐渐降低、相对粘度逐渐增大;当Np≥6时,羧基阴离子基团置于吸附层最外围,吸附层厚度近似等于PEO侧链长度,聚合物在固体表面形成空间排斥为主、静电排斥为辅的吸附状态;吸附聚合物分子密度过低或过高均不能起到良好的空间屏蔽或阻隔效应;吸附在固体粒子表面聚合物应该具有适宜的吸附-脱附自平衡能力.     

显微-反射傅里叶变换红外光谱研究油酸钠与胶磷矿吸附机理

红外光谱已经成为浮选药剂作用机理研究的最重要手段之一。由于矿物本身具有较强的红外吸收,传统溴化钾压片透射光谱很难检测到矿物表面吸附药剂的微弱红外信号。采用显微-傅里叶变换红外光谱仪的反射模式,测定了不同浓度油酸钠在胶磷矿表面的吸附形式,并观察了吸附形貌。结果表明,与透射红外光谱相比,反射红外光谱对表面有更高的灵敏度,能更好地揭示实际浮选药剂浓度下的吸附机理。碱性条件下当油酸钠浓度较低时,油酸离子与表面晶格钙离子发生化学吸附,吸收峰在1 552 cm-1,同时也存在油酸钙沉淀的物理吸附,吸收峰在1 570和1 535 cm-1;当油酸钠浓度超过临界胶束浓度时,胶束使得胶磷矿表面亲水,导致油酸钠溶液残留在表面,吸收峰在1 560 cm-1,掩盖了其他吸收峰;表面经水洗涤后药剂吸收峰强度大幅减弱,是由于残留的油酸钠和物理吸附的油酸钙被洗掉。另外,随着油酸钠浓度增大,药剂二维形貌由点状吸附聚集为片状吸附,覆盖面积增大,但并不是完全覆盖,这与矿物表面异质性有关。以上研究结果有利于理解磷矿石提磷或铁矿石脱磷浮选体系中捕收剂与胶磷矿的作用机理。     

Beryllium oxide (BeO) nanotube provides excellent surface towards adenine adsorption: A dispersion-corrected DFT study in gas and water phases

Zigzag (5, 0) BeO nanotube (BeONT) has been examined in detail towards adsorption properties of adenine nucleobase on its surface via D2-DFT calculation method in the gas and water phases. A detailed surface study reveals that there are four orientations for nucleobase adsorption that none of the vibrational spectrums demonstrated imaginary frequency, recognizing that all of the relaxed structures are at the minimum of energy. The minimum and maximum adsorption energies are both in chemisorption regime with calculated values of −140 (−118 BSSE corrected) and −191 (−168 BSSE corrected) in the gas phase, and −181 and −310 kJ/mol in the water phase, using meta-hybrid functional (ꞷB97XD) and 6-31G** basis set. For all positions, BeONT showed p-type semiconducting property because of receiving electronic charge from adenine molecule. Our findings suggest that BeONT could be used as a possible strong carrier for adenine molecule in practical applications.     

纳米SiO2/十二烷基氨基丙酸钠协同稳定的pH响应性Pickering乳状液

用纳米SiO₂颗粒与微量氨基酸型两性表面活性剂十二烷基氨基丙酸钠作复合乳化剂, 以正癸烷为油相, 制备了pH响应性O/W型Pickering乳状液. 室温下该乳状液在pH≤4.0 时稳定, 在pH≥6.0时不稳定, 因此, 可以通过改变水相的pH值使乳状液在稳定和破乳之间多次循环. 在酸性水介质中, 氨基酸型两性表面活性剂分子呈阳离子状态, 可通过静电作用吸附到带负电荷的SiO₂颗粒表面, 产生原位疏水化作用, 使其转变为表面活性颗粒; 而在中性和碱性水介质中, 氨基酸型两性表面活性剂呈两性或阴离子状态, 不能产生原位疏水化作用, 因而导致乳状液破乳. 相关作用机理通过吸附量、 Zeta电位及接触角等实验数据得以论证. 该刺激-响应性Pickering乳状液在乳液聚合、 油品输送以及燃料生产等领域具有重要的应用价值.     

Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces

In this review we survey the contributions that molecular beam experiments have provided to our understanding of the dynamics and kinetics of chemical interactions of gas molecules with solid surfaces. First, we describe the experimental details of the different instrumental setups and approaches available for the study of these systems under the ultrahigh vacuum conditions and with the model planar surfaces often used in modern surface-science experiments. Next, a discussion is provided of the most important fundamental aspects of the dynamics of chemical adsorption that have been elucidated with the help of molecular beam experiments, which include the development of potential energy surfaces, the determination of the different channels for energy exchange between the incoming molecules and the surface, the identification of adsorption precursor states, the understanding of dissociative chemisorption, the determination of the contributions of corrugation, steps, and other structural details of the surface to the adsorption process, the effect to molecular steering, the identification of avenues for assisting adsorption, and the molecular details associated with the kinetics of the uptake of adsorbates as a function of coverage. We follow with a summary of the work directed at the determination of kinetic parameters and mechanistic details of surface reactions associated with catalysis, mostly those promoted by late transition metals. This discussion we initiate with an overview of what has been learned about simple bimolecular reactions such as the oxidation of CO and H₂ with O₂ and the reaction of CO with NO, and continue with the review of the studies of more complex systems such as the oxidation of alcohols, the conversion of organic acids, the hydrogenation and isomerization of olefins, and the oxidative activation of alkanes under conditions of short contact times. 6 Reactions on supported nanoparticles: Materials gap, 7 Low-probability reactions: Pressure gap of this review deal with the advances made in the use of molecular beams with more realistic models for catalysis, using surfaces comprised of metal nanoparticles dispersed on the oxide surfaces used as catalyst support and high-flux beams to approach the pressures used in catalysis. The next section deals with the study of systems associated with fields other than catalysis, mainly with the etching and oxidation of semiconductor surfaces and with the chemistry used to grow thin solid films by chemical means (chemical vapor deposition, CVD, or atomic layer deposition, ALD). We end with a personal assessment of the past accomplishments, present state, and future promise of the use of molecular beams for the study of the kinetics of surface reactions relevant to practical applications.     

水分子在Yn (n=2-8)团簇表面的分子吸附与解离吸附

运用密度泛函理论,对H2O在Yn (n=2-8) 团簇表面的分子吸附与解离吸附两种模式进行了结构优化,电子性质分析。结果表明：分子吸附中H2O倾向于O端吸附于Y-Y原子桥位,而解离吸附中H2O解离的H, O原子倾向于吸附于Yn团簇的面位。两种吸附模式都导致了（解离吸附n=4, 5除外）主团簇Y原子平均键长增大。分子吸附和解离吸附的吸附强度和化学活性都随尺寸增加而增大。解离吸附中体系的稳定性明显高于分子吸附,且与体系的电子壳层效应密切相关。