镁铝水滑石及其改性产物的表面性质的研究

采用共沉淀法制备了n_Mg/n_Al比为2∶1镁铝水滑石(Mg/Al-HTlc),经500 ℃焙烧后得到镁铝复合氧化物(C-HT),并用十二烷基苯磺酸钠(SDBS)对复合氧化物进行了改性(M-HT)。通过反相气相色谱法(IGC)对Mg/Al-HTlc、C-HT和M-HT的表面性质进行了研究,定量计算了表面吸附自由能、表面能色散组分以及表面自由能特征分量。结果表明,三者的表面自由能以及色散能的大小顺序为：C-HT＞Mg/Al-HTlc＞M-HT;温度对非极性分子与Mg/Al-HTlc间的色散能影响不大,而非极性分子与C-HT和M-HT间的色散能均随温度的升高而降低;极性分子与固定相的吸附作用包括色散能和吸附自由能特征分量两部分,表面改性会使Mg/Al-HTlc的自由能特征分量降低。     

反相气相色谱法探究铜镁铝水滑石的表面性质

采用共沉淀法合成了Cu_xMg_3-xAl-LDHs (x＝0～3), 利用FTIR 及IGC 法(反相气相色谱法)对合成的样品进行测试和表征, 并结合计算机模拟的结果来探讨铜镁铝水滑石的表面性质. 结果表明, 随 Cu²⁺含量的增加, 铜镁铝水滑石表面吸附自由能及表面能色散组分增加, 稳定性下降, 这可能由于Cu²⁺本身具有的Jahn-Teller 畸变会很大程度地影响层板的稳定性, 导致含铜水滑石体系的稳定性降低; 随着Cu²⁺含量的增加, 水滑石表面碱性先减小后增大.     

水滑石无机阴离子交换剂的合成与表征

采用水热法制成了镁铝碳酸盐型、镁铝硝酸盐型、镁铝盐酸盐型、镁铝羟基型等插层镁铝类水滑石,比较了层间含不同阴离子类水滑石的结构差异和高温热处理后的结构稳定性.通过离子交换方式以镁铝羟基型为基材插层组装无机阴离子基团MoO42-、WO42-、CO32-和NO3-制得不同的阴离子插层类水滑石.通过XRD、TEM、XPS和热分析方法对镁铝类水滑石和阴离子插层类水滑石进行了表征.     

二氧化碳氧化丙烷制丙烯催化反应的研究铬镁铝复合氧化物催化剂的制备、表面微量吸附量热及催化性能

以共沉淀法合成的铬镁铝类水滑石为前体,制备了一系列不同原子比的铬镁铝复合氧化物,研究了其对二氧化碳氧化丙烷制丙烯反应的催化性能.采用微量吸附量热技术,以CO2和NH3为探针分子定量地表征了样品表面酸碱中心的强度和数量,并与其催化性能进行了关联.结果表明,Cr:Mg:Al原子比为1:1:1的催化剂具有较大的比表面积(94.5m2/g),样品中Mg(Al1.5Cr05)O4物相的含量最多.样品表面存在数量较多强度较强的酸性中心和数量最少强度较弱的碱性中心,对NH3吸附,它的吸附热为145 kJ/mol,吸附覆盖度为3.55μmol/m2;对CO2吸附,它的吸附热为115kJ/mol,吸附覆盖度为0.063μmol/m2.该样品的催化活性最高,在温度为650℃,CO2/C3H8摩尔比为3.6,GHSV(C3H8)为3000 h-1时,C3H8的转化率为22.8%,C3H6的选择性为83.5%,收率为19.1%.     

焙烧态镁铝水滑石对诺氟沙星的吸附行为研究

采用共沉淀法合成镁铝水滑石(LDH),用X-射线衍射(XRD)、扫描电镜(SEM)等表征了产物,研究了400℃焙烧后LDH(LDO)的结构、成分及吸附率的变化,通过静态吸附实验考察了LDO对诺氟沙星的吸附性能。结果表明,在固液比1∶500、pH=5.0、吸附温度25℃、离子强度0.1 mol/L的条件下吸附1 h对诺氟沙星(20 mg/L)的吸附率达91.25%。吸附过程符合Langmuir等温线方程,理论平衡吸附量达到32.05 mg/g,推断焙烧态镁铝水滑石对诺氟沙星的吸附是以表面吸附为主的自发反应。     

阴-非离子表面活性剂复合改性水滑石的表面性质研究

采用十二烷基苯磺酸钠(SDBS)、吐温-80(Tween-80)及两种表面活性剂复合改性镁铝水滑石,得到SDBS-LDHs,TweenLDHs及SDBS/Tween-LDHs 3种改性水滑石。利用反相气相色谱法(IGC)对样品进行表面性质的研究,定量计算了表面吸附自由能(ΔG0)和表面能色散组分(γs d)。结果表明,改性材料的ΔG0与γs d值均比未处理的镁铝水滑石小,其中阴-非离子表面活性剂复合改性后的水滑石的ΔG0与γs d值最小,说明阴-非离子表面活性剂复合改性水滑石较单一改性水滑石更有利于提高材料的稳定性。此外,各类水滑石的γs d值均随着温度的升高而减小,因此,在制备聚合物/水滑石类材料时,可以利用提高温度来改善其与聚合物的相容性。     

镁铝类水滑石的合成、表征及其催化丙酮缩合性能

采用共沉淀-水热法合成了一系列的类水滑石样品.用XRD、TEM等表征了合成样品的结构及表面形貌;用NH3-TPD、CO2-TPD测试样品表面酸碱性质,优化了镁铝水滑石的合成条件,重点考察了镁铝比对合成样品晶形的影响和样品表面酸碱性变化的规律,阐述了层板上原子配位分布的微观结构,以及不同镁铝比的类水滑石在催化丙酮缩合制备双丙酮醇反应中催化性能.     

高荧光性含锌类水滑石研究

本研究将适量锌离子(II)取代镁铝水滑石中的镁离子(II), 以及将一定量的8-羟基喹啉(8-hydroxyquinoline)分散于镁铝水滑石层间的亲油性阴离子中, 使与其板层表面上的锌离子配位, 经共沉淀法, 合成、组装得到一类迄今未见报道的具高荧光性的类水滑石(Zn-HTLC)荧光材料. 采用荧光光谱、红外光谱、紫外光谱、X射线衍射和热分析等对其进行了表征. 研究表明, 这种类水滑石在紫外光下可发出强烈的蓝绿色荧光(501 nm), 荧光强度高达4.5×10⁵ a.u., 说明锌离子(II)分散于类水滑石的氢氧化镁板层中, 可有效防止发光结构单元的荧光猝灭, 而且溶于层间阴离子中的配体与板层上的锌离子(II)配位所形成的特殊组装结构, 增强了发光中心的不对称性, 也是其具有高荧光性的可能原因. 热分析结果显示, 这种类水滑石耐热性强, 有望应用于各种功能性荧光材料.     

谷氨酸插层水滑石吸附水中铅离子

采用共沉淀法合成了谷氨酸插层镁铝类水滑石(LDH),对所制备的试样进行了X-射线衍射和红外光谱表征,对LDH去除水中铅离子的能力进行了讨论,研究了吸附过程的吸附动力学和吸附等温线。结果表明,谷氨酸能嵌入镁铝水滑石的层间,该插层水滑石能有效吸附水中铅离子,吸附过程符合准二级动力学模型,吸附等温曲线可用Langmuir模型来描述,吸附量可达68.49mg/g。     

不同锌铝比水滑石的合成及吸附脱除水中邻苯二甲酸性能的研究

采用共沉淀法合成一系列具有不同锌铝比的水滑石,并利用X射线衍射（XRD）、扫描电镜（SEM）、热重（TG）、氮气吸脱附及电感耦合等离子体质谱（ICP-MS）等表征手段对其结构与组成进行了测试。将上述水滑石材料用于吸附脱除水中邻苯二甲酸污染物,考察了不同锌铝比水滑石吸附邻苯二甲酸性能的差异。结果表明,在较低锌铝比时,随着水滑石锌铝比的增加,其对邻苯二甲酸的吸附量逐渐增大;当锌铝比较大时（>6）,随着锌铝比的增加,水滑石的吸附量基本保持不变。进一步选取锌铝比为6的水滑石,分别对其吸附邻苯二甲酸的动力学和热力学进行了研究,发现其吸附等温线和吸附动力学数据分别符合Freundlich等温吸附模型和准二级动力学模型,且循环吸附性能较好。     

Use of inverse gas chromatography to characterize cotton fabrics and their interactions with fragrance molecules at controlled relative humidity

The present work focused on the surface characterization and fragrance interactions of a common cotton towel at different relative humidities (RHs) using inverse gas chromatography (IGC) and dynamic vapour sorption. The sigmoidal water sorption isotherms showed a maximum of 16% (w/w) water uptake with limited swelling at 100% RH. This means that water interacts strongly with cotton and might change its initial physico-chemical properties. The same cotton towel was then packed in a glass column and characterized by IGC at different relative humidities, calculating the dispersive and specific surface energy components. The dispersive component of the surface energy decreases slightly as a function of relative humidity (42 mJ/m2 at 0% RH to 36 mJ/m2 at 80% RH) which would be expected from swelling of the humidified cotton. The Gutmann's donor constant Kd increased from 0.28 kJ/mol at 0% RH to 0.42 kJ/mol at 80% RH, indicating that a greater hydrophilic surface exists at 80% RH, which is also as expected. Water, undecane and four fragrance molecules (dimetol, benzyl acetate, decanal and phenylethanol) were used to investigate cotton-fragrance interactions between 0 and 80% RH. The adsorption enthalpies and the Henry's constants were calculated and are discussed. The higher values for the adsorption enthalpies of polar molecules such as dimetol and phenylethanol suggest the presence of hydrogen bonds as the main adsorption mechanism. The Henry's constant of dimetol was also determined by headspace gas chromatography measurements at 20% RH, giving a similar value (230 nmol/Pa g by IGC and 130 nmol/Pa g by headspace GC), supporting the usefulness of IGC for such determinations. This work confirms the usefulness of chromatographic methods to investigate biopolymers such as textiles, starches and hairs.     

DOPA醌在Cu（100）表面吸附的密度泛函理论研究

采用广义梯度密度泛函理论(GGA)的BLYP方法结合周期性平板模型,以原子簇Cu41为模拟表面,对DOPA醌分子在Cu(100)表面不同位置的吸附模型进行了构型优化、能量计算以及Mulliken布居分析,结果表明通过相邻的羰基垂直吸附在表面的桥位是其最佳吸附方式,吸附能为247.2310kJ/mol;其次为顶位、顶位R45和穴位,吸附能分别为227.7162kJ/mol、220.7305kJ/mol和217.8456kJ/mol。Mulliken布居分析结果表明整个吸附体系发生了由Cu原子向DOPA醌分子的电荷转移。     

Surface characterization and London dispersive surface free energy of functionalized single-walled carbon nanotubes with a blend of polytetrafluoroethylene by inverse gas chromatography

The SWCNTs and SWCNT-polytetrafluoroethylene (PTFE) blend were prepared by using simple reaction mixture in the presence of chromosorb (SiO₂). Surface morphology of SWCNTs and (SWCNT-PTFE) blend was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and surface BET analysis. In addition, the surface thermodynamic properties of n-alkanes and polar probe net retention volumes are measured by inverse gas chromatography (IGC). The London dispersive surface free energy values were found to be decreased linearly with increase of temperature. The specific component of the surface free energy of adsorption for the polar probes was obtained using the Donnet-Park method. The surface character “S” value (K_b/K_a) at SWCNTs was found to be 0.74, and SWCNT-PTFE blend surface character value was found to be 0.86. This result demonstrates that the (SWCNT-PTFE) blend surface contains relatively more acidic sites then that of SWCNT surface. Therefore, the IGC results provide useful complementary information on the (SWCNT-PTFE) blend surface.     

A study of the adsorption activities of silanol surface structures on a fused silica model substrate by combining 29Si CP MAS NMR and inverse gas chromatographic data

The possibilities of inverse gas-solid chromatography (IGC) in obtaining chromatographic data on fumed silica were examined. Aerosil A-200, a fused silica model substrate in ²⁹Si nuclear magnetic resonance analysis, was trimethylsilylated to different degrees. IGC was used to very reproducibly determine the free specific energies of adsorption of several functionalized probe solutes. Hydrogen bonding solutes have a free specific energy of adsorption that is at least about 50% higher than that of non-hydrogen bonding probe solutes. NMR was used in combination with elemental analysis to calculate surface concentrations of the different chemical surface structures. IGC data and surface concentrations were combined in order to determine the contribution of each type of surface structure to the total free specific adsorption energy. It could be concluded that residual silanols from the reaction of dihydroxydi-siloxysiloxane (Q₂ groups) with trimethylchlorosilane possess a higher adsorption activity than the silanols initially present.     

反相气相色谱法表征1-烯丙基-3-甲基氯代咪唑离子液体的表面性质

采用反相气相色谱(IGC)技术研究了不同温度下1-烯丙基-3-甲基氯代咪唑(［AMIM］Cl)的表面性质。以正己烷、正庚烷、正辛烷和正壬烷作为非极性探针分子测定［AMIM］Cl在343.15、353.15、363.15和373.15 K温度下的表面色散自由能;以二氯甲烷、三氯甲烷、丙酮、乙酸乙酯、四氢呋喃作为极性探针分子测定离子液体Lewis酸碱性质,并测定了吸附自由能和吸附自由焓变等热动力学参数。实验结果表明,［AMIM］Cl的酸解离平衡常数Ka为0.34,碱解离平衡常数Kb为1.68,其表面呈Lewis两性偏碱性特点。在343.15、353.15、363.15和373.15 K温度下,［AMIM］Cl的表面色散自由能分别为52.26、50.82、46.08和42.05 mJ/m2。这一结果对研究离子液体的表面性质及应用有指导作用。     

How silanization of silica particles affects the adsorption of PDMS chains on its surface

A series of six fumed silica types, with different surface areas in the 50–400 m²/g range, were modified by grafting with trimethylchlorosilane. The grafting reaction was controlled by elemental analyses, surface hydroxyl titration, and combustion techniques. The silica surface energy was determined as a function of silanization degree by inverse gas chromatography (IGC). Adsorption of a series of poly(dimethylsiloxane) elastomers with molecular weights ranging between 4 and 420 kg/mol on silica was followed using flow microcalorimeter (FMC). IGC results show that free adsorption energies of two series of alkanes and siloxanes as well as the dispersive component of the surface energy were found to decrease monotonously with surface silanization and so does the polymer molar heat of adsorption. FMC results indicate, however, that the conformation of the macromolecules on silica depends on the silica surface area but remains unaffected by the surface treatments. A given polymer chain was found to remain adsorbed on the surface preserving its same conformation until its molar heat of adsorption falls bellow a critical value. These findings offer a better monitoring of surface–polymer interactions as it defined a comprehensive relationship between the degree of modifications of the filler surface and polymer adsorption conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Adsorption and Decomposition Mechanism of 1,1‐Diamino‐2,2‐dinitroethylene on Al(111) Surface by Periodic DFT Calculations

The adsorption of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) molecule on the Al(111) surface was investigated by the generalized gradient approximation (GGA) of density functional theory (DFT). The calculations employ a supercell (4×4×2) slab model and three‐dimensional periodic boundary conditions. The strong attractive forces between oxygen and aluminum atoms induce the N? O bond breaking of the FOX‐7. Subsequently, the dissociated oxygen atoms and radical fragment of FOX‐7 oxidize the Al surface. The largest adsorption energy is ?940.5 kJ/mol. Most of charge transfer is 3.31e from the Al surface to the fragment of FOX‐7 molecule. We also investigated the adsorption and decomposition mechanism of FOX‐7 molecule on the Al(111) surface. The activation energy for the dissociation steps of P2 con?guration is as large as 428.8 kJ/mol, while activation energies of other con?gurations are much smaller, in range of 2.4 to 147.7 kJ/mol.     

Adsorption of methyl orange on nanoparticles of a synthetic zeolite NaA/CuO

CuO supported on an NaA zeolite (CuO/NaA) was prepared with an NaA zeolite through the ion-exchange (CuO/NaA) method. The morphology and the physicochemical properties of the prepared samples were investigated by XRD, MEB, and EDS. The various parameters, such as contact time, catalyst dose, initial dye concentration, initial pH, and temperature, influencing the adsorption of methyl orange (MO) were optimized. The MO adsorption equilibrium was reached after 240 min of contact time. Removal of MO is better at neutral pH than in acidic and alkaline solutions. Among the tested models, the equilibrium adsorption data are well fitted by the Langmuir isotherm. The adsorption kinetics is best described by the pseudo-second-order model. The evaluation of the thermodynamic parameters, i.e. ΔG^o, ΔH^o, and ΔS^o, revealed that MO adsorption was spontaneous, while the activation energy (20.98 kJ/mol) indicates a physical adsorption. The photodegradation of MO decreased from 100 mg/L down to 2 mg/L when the solution is exposed to visible light.     

Adsorption of tetracycline using CuCoFe2O4@Chitosan as a new and green magnetic nanohybrid adsorbent from aqueous solutions: Isotherm,kinetic and thermodynamic study

Utilizing a new microwave-assisted method, CuCoFe₂O₄@Chitosan (Ch) was synthesized as a very strong, magnetically separable nano-adsorbent. The magnetic nanohybrid adsorbent was characterized by FESEM (Field emission scanning electron microscopy), EDS (energy dispersive X-ray), Mapping & Linescan, BET (Brunauer-Emmett-Teller), FTIR (Fourier-transform infrared spectroscopy), XRD (X-ray diffraction analysis), TGA (Thermogravimetric analysis), and VSM (Vibrating Sample Magnetometer) techniques. Then, the adsorption process of Tetracycline (TC) was investigated. The highest percentage of pollutant adsorption on the synthetic and real samples was recorded at an initial concentration of 5 mg/L, pH 3.5, contact time of 20 min, the dose of 0.4 g/L, and temperature of 25 °C, 93.07 %, and 67%, respectively. The TC adsorption process via the synthesized magnetic nanocomposite was consistent with the Freundlich isotherm model (R² = 0.992) and pseudo-second-order kinetic (K₂ = 0.267). The outcomes of thermodynamic analyses, which included entropy changes (ΔS = 10.122 J/mol.k), enthalpy changes (ΔH = ?1.975 kJ/mol), and the Gibbs negative free energy (ΔG = ?4.992 kJ/mol), revealed that the adsorption process was spontaneous, favorable, and exothermic. The good magnetic properties allow easy separation after the adsorption operation. Finally, the efficiency of the nano-adsorbent in the removal process was 82.16% after four adsorption–desorption cycles. Some advantages of this research are a fast and green method for synthesis of adsorbent, fast kinetic, and magnetic properties to easy separation.     

反气相色谱法研究煤直接液化残渣经分级提取前后的表面性质变化

采用反气相色谱法（IGC）分别对煤直接液化残渣（DCLR）脱灰处理后不溶物、正己烷不溶物、甲苯不溶物、四氢呋喃不溶物的表面性质进行表征。基于非极性探针净保留体积V_n分别采用Dorris-Gray方法和Schultz方法得到表面色散自由能,基于极性探针V_n得到吸附焓△H^sp,并通过△H^sp作图计算得到酸常数K_a和碱常数K_b。结果表明,经溶剂分级提取后表面色散自由能、K_a和K_b均发生明显变化。而DCLR呈现两性偏碱性这一特征并未随分级提取发生改变。IGC作为一种动力学吸附技术,可快速准确表征DCLR在经分级提取过程中表面性质的变化,相同温度下应用Dorris-Gray方法得到DCLR表面色散自由能略高于Schultz方法。