Heats of immersion of titanium dioxide pigments in alcohol—water mixtures

The heats of immersion of partially dried anatase and rutile pigments in mixtures of water with methanol, ethanol, and n-propanol were measured by a differential calorimetric method. The anatase heats of immersion could best be explained by assuming preferential adsorption of the alcohols, the effect being greatest for n-propanol The rutile pigment, however, appeared to adsorb water preferentially in methanol—water and ethanol—water mixtures over the whole concentration range. In propanol—water mixtures the rutile pigment preferentially adsorbed water below an alcohol mol fraction of 0.25, and preferentially adsorbed propanol at mol fractions of alcohol greater than 0.25. The differences in behaviour between the two pigments may be explained qualitatively from the point of view of their surface morphology.     

不同醇类对磷钨酸催化超临界醇解液化木屑的影响

以可溶解于醇类的磷钨酸为催化剂,在超临界醇体系下液化木屑,探讨甲醇、乙醇、正丙醇、异丙醇等不同醇类溶剂对木屑醇解液化的影响,同时采用FT-IR和GC-MS等对液化产物进行了表征分析。结果表明,反应压力和溶剂的极性大小对木屑的液化效率以及液化产物影响显著。甲醇、乙醇、正丙醇、异丙醇反应体系的液化率和主要液化产物酯类化合物的含量比率,分别为54.75%和43.759%、90.29%和23.531%、85.90%和41.761%、89.15%和28.619%,特别在甲醇体系中,乙酰丙酸甲酯的含量高达33.374%;在异丙醇体系中酚类化合物可达到24.342%;醛类化合物只出现在甲醇体系中。在正丙醇体系中没有酚类产物,表明极性最小的正丙醇,提供很少的H*,更不容易将木质素降解。     

Simulating of alcohol adsorption in slitlike micropores of active carbon by the molecular dynamics method

Benzene, methanol, ethanol, and 1,3-propanediol adsorption in model pores of active carbon is studied by the molecular dynamics method using the OPLSAA universal force field with allowance for the microheterogeneous structure of the carbon. It is shown that, in a slitlike pore with a width and a diameter of 0.7 and 3 nm, respectively, adsorbate molecules are, on average, located in parallel with pore walls and have a constant deviation from this position. When few molecules are contained in a limited pore space, they are located independently of one another in two different layers; however, as their concentration increases, initially, aggregates bonded (in the case of alcohols) through hydrogen bonds and, subsequently, dense layers are formed that strongly affect one another.     

The effect of F-doping and temperature on the structural and textural evolution of mesoporous TiO2 powders

Mesoporous F⁻-doped TiO₂ powders were prepared by hydrolysis of titanium tetraisopropoxide (TTIP) in a mixed NH₄F-H₂O solution. Effects of F⁻ ion content and calcination temperatures on the phase composition and porosity of mesoporous titania were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and BET surface areas. The results showed the BET surface area (S_BET) of the pure and doped powders dried at 100°C ranged from 260 to 310 m²/g as determined by nitrogen adsorption. With increasing calcination temperatures, the S_BET values of the calcined titania powders decreased due to the increase in crystalline size. The pore size distribution was bimodal with fine intra-particle pore and larger inter-particle pore as determined by nitrogen adsorption isotherms. The peak pore diameter of intra-particle pore increases with increasing F⁻ ion content. At 700°C, all the titania powders exhibit monomodal pore size distributions due to the complete collapse of the intra-particle pores. The crystallization of anatase was obviously enhanced due to F⁻-doping at 400°C and 500°C. Moreover, with increasing F⁻ ion concent, F⁻ ions not only suppressed the formation of brookite phase at low temperature, but also prevented phase transition of anatase to rutile at high temperature.     

Permeation of Liquids through Inorganic Nanofiltration Membranes

Inorganic nanofiltration membranes were prepared using silica-zirconia composite sols by the sol-gel method and applied for the permeation experiments of nonaqueous solutions. Pure solvent permeabilities of methanol, ethanol, and 1-propanol were measured at temperatures from 25 to 60 degrees C. For membranes having pore sizes as large as 70 nm, the permeation mechanism of alcohols obeys the viscous flow mechanism irrespective of types of alcohols. On the other hand, the permeation mechanism through porous silica-zirconia membranes having pore diameters of 1 to 5 nm was found to be different from the viscous flow mechanism; small molecules showed larger permeabilities than large molecules. Activation energies of solvent permeability were found to be larger for large molecules and for membranes of smaller pore size. Copyright 2000 Academic Press.     

Factors influencing the transport of short-chain alcohols through mesoporous gamma-alumina membranes

The pressure-driven transport of water, ethanol, and 1-propanol through supported gamma-alumina membranes with different pore diameters is reported. Water and alcohols had similar permeabilities when they were transported through gamma-alumina membranes with average pore diameters of 4.4 and 6.0 nm, and the permeability coefficient was found to be proportional to the square of pore size, in accordance with a viscous flow mechanism. For transport through membranes with an average diameter of 3.2 nm, the behavior of water was in accordance with the viscous flow mechanism, but the permeability of the membrane for ethanol and 1-propanol was much smaller than expected and could not be explained in terms of viscous flow. Although the low permeability of the membrane with 3.2 nm pores for ethanol and 1-propanol was partly due to the presence of small amounts of water in the alcohols, the permeability coefficients were still substantially smaller when water was absent. This intrinsic difference between water and alcohol may be due to differences in molecular size, chemisorption of alcohols on the oxide pore wall, which would lead to a reduction of the effective pore size, and/or a certain degree of translational ordering of the alcohol molecules inside the membrane pores, which leads to an effectively higher viscosity and, therefore, to a higher transport resistance.     

Permporometry characterization of microporous ceramic membranes

An evaluation of nano-order pore size of membranes was carried out using permporometry, the basic principle of which is based on capillary condensation of vapor and the blocking effect of permeation of a non-condensable gas. A computer-controlled apparatus was constructed, where liquid was injected by a syringe pump and nitrogen was used as a carrier, and was applied to the evaluation of the pore size of ceramic membranes prepared from a silica–zirconia composite. The pore size distribution, based on the Kelvin equation (Kelvin diameter), was evaluated over a range of 0.5–30 nm, using water as a condensable vapor. Vapors used in the present study were water, methanol, ethanol, isopropanol, carbon tetrachloride, and hexane. For the case of relatively large pore sizes (larger than 1 nm, based on water vapor), pore size distribution obtained by water vapor agreed very well with those by carbon tetrachloride and hexane. However, pore sizes measured using alcohols were found to be smaller than those determined by water vapor. For the case of pore sizes smaller than 1 nm, the adsorption layer before capillary condensation appears to play an important role.     

Volumetric and Surface Properties of Short Chain Alcohols in Aqueous Solution–Air Systems at 293?K

From measurements of the surface tension, density, viscosity and light scattering of aqueous solutions of methanol, ethanol and propanol at 293?K, their activity in the surface monolayer, surface excess concentration, and apparent and partial molar volume were determined. The surface excess concentration of alcohols at the water?Cair interface was determined from the Gibbs equation by using both the alcohol's activity and their molar fraction in the bulk phase and recalculated by using the Guggenheim?CAdam equation. The values of the surface excess concentration determined from the Gibbs equation were also applied to determine the standard Gibbs energy of alcohol adsorption at the water?Cair interface from Langmuir??s equation and compared to those determined from that of Aronson and Rosen.     

Targeted Functionalization of Porous Materials for Separation of Alcohol/Water Mixtures by Modular Assembly

Three isoreticular hydrogen‐bonded frameworks with functionalized pore structures were constructed by a modular self‐assembly process in which a series of amino acids with various substituents serve as facile exchange subassemblies to decorate the pore wall. The ordered amino acid side‐chain groups in the pore channels play an important role in determining the adsorption behavior of the framework materials, and ensure exclusive adsorption of methanol/water over ethanol. Gas‐chromatographic separation experiments demonstrated that alcohols can be efficiently separated from ternary water/methanol/ethanol mixtures and revealed a key influence of the adsorbate–host framework interaction on the practical separation performance of mixtures.     

Pd/Fe3O4-C催化剂对甲醇、乙醇和丙醇氧化的电催化活性

制备对醇氧化反应具有优异电活性的钯催化剂是醇燃料电池研究的重要内容。本文用硼氢化钠还原法制备了钯纳米颗粒, 然后沉积在Fe3O4/C复合物表面, 得到了不同Fe₃O₄负载量的Pd/Fe₃O₄-C催化剂. 透射电镜（TEM）图显示钯纳米颗粒均匀地分散在Fe₃O₄/C表面. 对制备好的Pd/Fe₃O₄-C催化剂进行了循环伏安法（CV）、计时电流（CA）和电化学阻抗谱（EIS）的测试, 研究了其在碱性介质中对C1-C3醇类（甲醇、乙醇和丙醇）氧化的电催化活性. 结果表明, 所制备的不同Fe₃O₄负载量的Pd/Fe₃O₄(2%)-C,Pd/Fe₃O₄(5%)-C, Pd/Fe₃O₄(10%)-C和Pd/C催化剂中, Pd/Fe₃O₄(5%)-C催化剂表现出最高的醇氧化电流密度. 依据循环伏安（CV）数据,Pd/Fe₃O₄(5%)-C催化剂对甲醇、乙醇、正丙醇和异丙醇氧化的阳极峰电流密度分别是Pd/C催化剂的1.7、1.4、1.7和1.3倍. Pd/Fe₃O₄(5%)-C催化剂对乙醇氧化的电荷传递电阻也远低于Pd/C催化剂. 制备的所有催化剂对C1-C3醇类电氧化的电流密度大小排序如下: 正丙醇﹥乙醇﹥甲醇﹥异丙醇. 此外, 碳粉中Fe₃O₄纳米颗粒的存在提高了钯纳米颗粒的电化学稳定性.     

Mesoporous zirconium titanium oxides. Part 1: Porosity modulation and adsorption properties of xerogels

A series of zirconium titanium oxide mesophases containing 33 atom % Zr have been prepared using carboxylic acids of different alkyl chain lengths (Cy ) from y=4-18 through organic-inorganic polymer phase segregation as the gel transition is approached. Thermal treatment of these transparent gels up to 450 degrees C eliminated the organic template, and domain coarsening occurred affording stable worm-hole mesoporous materials of homogeneous composition and pore diameters varying from about 3 to 4 nm in fine increments. With such materials, it was subsequently possible to precisely study the adsorption of vanadium oxo-anions and cations from aqueous solutions and, more particularly, probe the kinetics of intraparticle mass transport as a function of the associated pore dimension. The kinetics of mass transport through the pore systems was investigated using aqueous vanadyl (VO2+) and orthovanadate (VO3(OH)2-) probe species at concentrations ranging from 10 to 200 ppm (0.2 to 4 mmol/L) and pH values of 0 and 10.5, respectively. In the case of both of these vanadium species, the zirconium titanate mesophases displayed relatively slow kinetics, taking in excess of about 500 min to achieve maximum uptake. By using a pseudo-second-order rate law, it was possible to extract the instantaneous and overall rate of the adsorption processes and then relate these to the pore diameters. Both the instantaneous and overall rates of adsorption increased with increasing surface area and pore diameter over the studied pore size range. However, the equilibrium adsorption capacity increased linearly with pore diameter only for the higher concentrations and was independent of pore diameter for the lower concentration. These results have been interpreted using a model in which discrete adsorption occurs at low concentrations and is then followed by multilayer adsorption at higher concentration.     

锐钛矿型纳米TiO2介孔粉体表面织构的研究

以硫酸钛和尿素为原料,聚乙二醇-1000为空间构造剂,104℃下经尿素水解均匀沉淀法研制颗粒分散均匀、粒径可控的高热稳定性锐钛矿型纳米TiO2介孔粉体,并对其晶相、颗粒大小、比表面积、形貌和孔道结构进行了表征.结果表明,未经任何热处理的TiO2粉体即为锐钛型晶相,颗粒为均匀分散的类球型颗粒,且颗粒间形成直通型的介孔孔道,其孔径在10～30nm之间.控制焙烧温度可以达到控制颗粒大小及形貌的目的,经850℃焙烧5h的样品仍保持锐钛矿型晶相,未出现向金红石型晶相转变的迹象.     

Surface analysis of cryofixation-vacuum-freeze-dried polyaluminum chloride-humic acid (PACl-HA) flocs

The powder of polyaluminum chloride-humic acid (PACl-HA) flocs was prepared by cryofixation-vacuum-freeze-drying method. The FTIR spectra show that some characteristic functional groups in polyaluminum chloride (PACl), humic acid (HA), and kaolin still existed in the dried flocs. X-ray diffractometry (XRD) patterns indicate that these flocs are amorphous. Nitrogen adsorption-desorption isotherms were obtained for different samples of the dried PACl-HA flocs. The BET specific surface area, BJH cumulative absorbed volume and BJH desorption average pore diameter of them were determined. The peak values of 8.4-11.2 nm (pore diameter) for pore size distribution (PSD) curves indicate that the pores of the dried flocs are mostly mesopores. The surface fractal dimensions D(s) and the corresponding fractal scales determined from both SEM images and nitrogen adsorption-desorption data sets reveal the multi-scale surface fractal properties of the dried PACl-HA flocs, which exhibited two distinct fractal regimes: a regime of low fractal dimensions (2.07-2.26) at higher scales (23-387 nm), mainly belonging to exterior surface scales, and a higher fractal dimensions (2.24-2.37) at lower scales (0.80-7.81 nm), falling in pore surface scales. Both HA addition and kaolin reduction in dried floc can decrease the irregularity and roughness of external surface. However, for the irregularity and roughness of pore surface, the addition of HA or kaolin in dried floc can increase them. Furthermore, some difference was found between the pore surface fractal dimensions D(s) calculated from nitrogen adsorption and desorption data. The pore surface D(s) values calculated through thermodynamic model were much greater than three.     

SAPO-34处理方法对吸附性能的影响

以二乙胺为结构导向剂, 在微波条件下合成了SAPO-34分子筛材料, 并分别在空气和氮气氛下1073 K焙烧. 考察了氮气氛下分子筛表面碳改性后对材料表面及水、甲醇和乙醇吸附性能的影响. 结果表明: 碳改性后SAPO-34比表面、孔容下降, 但孔径趋于均一. 与SAPO-34样品相比, 碳改性后SAPO-34吸水量从0.295 g/g降低到0.180 g/g, 甲醇/乙醇的吸附比从1.42提高到2.81.     

以无机铝盐为前驱体用溶胶凝胶法合成中孔氧化铝

以水合硝酸铝(Al(NO3)3·9H2O)为前驱体, 通过乙醇介质中环氧丙烷的开环反应促使形成了透明的块状氧化铝凝胶. 凝胶在常压下干燥并于700 ℃焙烧后得到中孔无定型氧化铝. 通过改变环氧丙烷的加入量实现了氧化铝孔径和孔体积等宏观结构性能的调节. 用扫描电镜(SEM)、傅立叶变换红外光谱(FI-IR)和差热分析(DTA)等方法对样品进行了表征. 由于合成中存在环氧丙烷开环产物作为液体模板剂的造孔作用, 在氧化铝凝胶中造成了孔分布曲线具有双峰分布的墨水瓶状孔. 反应过程中pH值的测定和红外光谱的表征结果都证明环氧丙烷是一种很好的质子消耗剂, 其开环促使铝离子水解聚合并形成凝胶网络结构. 同时根据表征结果对环氧丙烷参与的溶胶凝胶氧化铝的合成机理进行了探讨.     

Development of an alcohol optode membrane based on fluorescence enhancement of fluorescein derivatives

A new type of optode membrane for the determination of alcohols, such as methanol, ethanol, propan-1-ol and propan-2-ol etc, is presented that can be exploited in optical and fibre-optic sensors. It is based on the use of a new lipophilic fluorescent reagent, namely fluorescein octadecyl ester (FODE), which is immobilized in a plasticized PVC membrane. The response mechanism relies on the fact that FODE can reversibly recognize alcohol molecules due to the hydrogen bonding formation between FODE and alcohol molecules. The analytical information in this membrane is the enhancement of the relative fluorescence intensity measured at 527 nm (463 nm, excitation). Under the optimum condition, the membrane has a wide measuring range for alcohol samples. The membrane has been applied to determine the concentration of ethanol in alcoholic drinks with satisfactory results.     

Effects of solvent on TEOS hydrolysis kinetics and silica particle size under basic conditions

In-situ liquid-state ²⁹Si nuclear magnetic resonance was used to investigate the temporal concentration changes during ammonia-catalyzed initial hydrolysis of tetraethyl orthosilicate in different solvents (methanol, ethanol, n-propanol, iso-propanol and n-butanol). Dynamic light scattering was employed to monitor simultaneous changes in the average diameter of silica particles and atomic force microscopy was used to image the particles within this time frame. Solvent effects on initial hydrolysis kinetics, size and polydispersity of silica particles were discussed in terms of polarity and hydrogen-bonding characteristics of the solvents. Initial hydrolysis rate and average particle size increased with molecular weight of the primary alcohols. In comparison, lower hydrolysis rate and larger particle size were obtained in the secondary alcohol. Exceptionally, reactions in methanol exhibited the highest hydrolysis rate and the smallest particle size. Ultimately, our investigation elaborated, and hence confirmed, the influences of chemical structure and nature of the solvent on the formation and growth of the silica particles under applied conditions.     

Porous structure of natural and modified clinoptilolites

The evaluation of the pore-size distribution (PSD) of natural and modified mesoporous zeolites, i.e., clinoptilolites is presented. We demonstrate the SEM results showing that the pores of fracture-type from 25-50 nm to 100 nm in size between clinoptilolite grains, as well as pores between crystal aggregates up to 500 nm in size are present in the studied material. The detailed distribution of pore sizes and tortuosity factor of the above-mentioned materials are determined from the adsorption-desorption isotherms of nitrogen measured volumetrically at 77 K. To obtain the reliable pore size distribution (PSD) of the above-mentioned materials both adsorption and desorption branches of the experimental hysteresis loop are described simultaneously by recently developed corrugated pore structure model (CPSM) of Androutsopoulos and Salmas. Evaluated pore size distributions are characterized by well-defined smooth peaks placed in the region of the mesoporosity. Moreover, the mean pore diameter calculated from the classical static measurement of nitrogen adsorption at 77 K correspond very well to the pore diameters from SEM, showing the applicability of the CPSM for characterization of the porosity of natural zeolites. We conclude that classical static adsorption measurements combined with the proper modeling of the capillary condensation/evaporation phenomena are a powerful method which can be applied for pore structure characterization of natural and modified clinoptilolites.     

Effect of anionic surfactant and short-chain alcohol mixtures on adsorption at quartz/water and water/air interfaces and the wettability of quartz

Measurements of the advancing contact angles for aqueous solutions of sodium dodecyl sulfate (SDDS) or sodium hexadecyl sulfonate (SHS) in mixtures with methanol, ethanol, or propanol on a quartz surface were carried out. On the basis of the obtained results and Young and Gibbs equations the critical surface tension of quartz wetting, the composition of the surface layer at the quartz-water interface, and the activity coefficients of the anionic surfactants and alcohols in this layer as well as the work of adhesion of aqueous solutions of anionic surfactant and alcohol mixtures to the quartz surface were determined. The analysis of the contact angle data showed that the wettability of quartz changed visibly only in the range of alcohol and anionic surfactant concentration at which these surface-active agents were present in the solution in the monomeric form. The analysis also showed that there was a linear dependence between the adhesion and the surface tension of aqueous solutions of anionic surfactant and alcohol mixtures. This dependence can be described by linear equations for which the constants depend on the anionic surfactant and alcohol concentrations. The slope of all linear dependence between adhesion and surface tension was positive. The critical surface tension of quartz wetting determined from this dependence by extrapolating the adhesion tension to the value equal to the surface tension (for contact angle equal zero) depends on the assumption whether the concentration of anionic surfactant or alcohol was constant. Its average value is equal to 29.95mN/m and it is considerably lower than the quartz surface tension. The positive slope of the adhesion-surface tension curves was explained by the possibility of the presence of liquid vapor film beyond the solution drop which settled on the quartz surface and the adsorption of surface-active agents at the quartz/monolayer water film-water interface. This conclusion was confirmed by the work of adhesion of aqueous solutions of anionic surfactants and short-chain alcohol mixtures to the quartz surface determined on the basis of the contact angle data and molar fraction of anionic surfactants and alcohols and their activity coefficient in the surface layer.     

Alcohol‐Vapor Inclusion in Single‐Crystal Adsorbents [MII2(bza)4(pyz)]n (M=Rh,Cu): Structural Study and Application to Separation Membranes

The vapor absorbency of the series of alcohols methanol, ethanol, 1‐propanol, 1‐butanol, and 1‐pentanol was characterized on the single‐crystal adsorbents [M^II₂(bza)₄(pyz)]_n (bza=benzoate, pyz=pyrazine, M=Rh ( 1 ), Cu ( 2 )). The crystal structures of all the alcohol inclusions were determined by single‐crystal X‐ray crystallography at 90 K. The crystal‐phase transition induced by guest adsorption occurred in the inclusion crystals except for 1‐propanol. A hydrogen‐bonded dimer of adsorbed alcohol was found in the methanol‐ and ethanol‐inclusion crystals, which is similar to a previous observation in 2 ?2EtOH (S. Takamizawa, T. Saito, T. Akatsuka, E. Nakata, Inorg. Chem. 2005 , 44, 1421–1424). In contrast, an isolated monomer was present in the channel for 1‐propanol, 1‐butanol, and 1‐pentanol inclusions. All adsorbed alcohols were stabilized by hydrophilic and/or hydrophobic interactions between host and guest. From the combined results of microscopic determination (crystal structure) and macroscopic observation (gas‐adsorption property), the observed transition induced by gas adsorption is explained by stepwise inclusion into the individual cavities, which is called the “step‐loading effect.” Alcohol/water separation was attempted by a pervaporation technique with microcrystals of 2 dispersed in a poly(dimethylsiloxane) membrane. In the alcohol/water separation, the membrane showed effective separation ability and gave separation factors (alcohol/water) of 5.6 and 4.7 for methanol and ethanol at room temperature, respectively.