2H-solid state NMR and DSC study of isobutyric acid in mesoporous silica materials

Solid state deuterium NMR has been used to study the molecular motion of d(6)-isobutyric acid (d(6)-iBA) in the pure (unconfined) state and confined in the cylindrical pores of two periodic mesoporous silica materials (MCM-41, pore size 3.3 nm and SBA-15, pore size 8 nm), and in a controlled pore glass (CPG-10-75, pore size ca. 10 nm). The line shape analysis of the spectra at different temperatures revealed three rotational states of the iBA molecules: liquid (fast anisotropic reorientation of the molecule), solid I (rotation of the methyl group) and solid II (no rotational motion on the time scale of the experiment). Transition temperatures between these states were determined from the temperature dependence of the fraction of molecules in these states. Whereas the solid I-solid II transition temperature is not affected by confinement, a significant lowering of the liquid-solid I transition temperature in the pores relative to the bulk acid was found for the three matrix materials, exhibiting an unusual dependence on pore size and pore morphology. Complementary DSC measurements on the same systems show that the rotational melting (solid I-liquid) of d(6)-iBA in the pores occurs at a temperature 20-45 K below the thermodynamic melting point. This finding indicated that the decoupling of rotational and translational degrees of freedom in phase transitions in confined systems previously found for benzene is not restricted to molecules with non-specific interactions, but represents a more general phenomenon.     

Thermodynamic, structural, and dynamic properties of supercooled water confined in mesoporous MCM-41 studied with calorimetric, neutron diffraction, and neutron spin echo measurements

Thermodynamic, structural, and dynamic properties of heavy water (D(2)O) confined in mesoporous silica glass MCM-41 C10, C12, and C14 were investigated by differential scanning calorimetry, neutron diffraction, and neutron spin echo (NSE) measurements, respectively. The DSC data showed that no crystallization of D(2)O confined in C10 occurs in a temperature range between 298 and 180 K, and that crystalline ice is formed at 204 and 221 K for C12 and C14, respectively. For C10, the neutron radial distribution functions of confined D(2)O suggested a structural change in the supercooled state between 223 and 173 K. For C10 sample, it has been found that the tetrahedral-like water structure is partially enhanced in the central part of pores at 173 K. For all the samples, the intermediate scattering functions from the NSE measurements are fitted by the Kohlrausch-Williams-Watts stretched exponential function which implies that confined supercooled D(2)O exhibits a wide distribution of relaxation times. For C10, C12, and C14 samples, between 298 and 240 K, the relaxation times of supercooled D(2)O follow remarkably well the Vogel-Fulcher-Tamman equation; for C10 sample, below 240 K, the relaxation times of nonfreezing D(2)O show an Arrhenius type behavior. From the present experimental results on calorimetric, structural, and dynamic properties, it has been concluded that supercooled D(2)O confined in MCM-41 C10 experiences a transition from high-density to low-density hydrogen-bonded structure at around 229 K.     

Local structure of a phase-separating binary mixture in a mesoporous glass matrix studied by small-angle neutron scattering

The mesoscopic structure of the binary system isobutyric acid + heavy water (D(2)O) confined in a porous glass (controlled-pore silica glass, mean pore width ca. 10 nm) was studied by small-angle neutron scattering at off-critical compositions in a temperature range above and below the upper critical solution point. The scattering data were analyzed in terms of a structure factor model similar to that proposed by Formisano and Teixeira [Eur. Phys. J. E 1, 1 (2000)], but allowing for both Ornstein-Zernike-type composition fluctuations and domainlike structures in the microphase-separated state of the pore liquid. The results indicate that the phase separation in the pores is shifted by ca. 10 K and spread out in temperature. Microphase separation is pictured as a transition from partial segregation at high temperature, due to the strong preferential adsorption of water at the pore wall, to a tube or capsule configuration of the two phases at low temperatures, depending on the overall composition of the pore liquid. Results for samples in which the composition of the pore liquid can vary with temperature due to equilibration with extra-pore liquid are consistent with this picture.     

Density measurement of 1-d confined water by small angle neutron scattering method: pore size and hydration level dependences

Small angle neutron scattering (SANS) is used to measure the absolute density of water contained in 1-D cylindrical pores of a silica material MCM-41-S with pore diameters of 19 and 15 A. By being able to suppress the homogeneous nucleation process inside the narrow pore, one can keep water in the liquid state down to at least 160 K. From a combined analysis of SANS data from both H(2)O and D(2)O hydrated samples, we determined the absolute value of the density of 1-D confined water. We found that the average density of water inside the fully hydrated 19 A pore is 8% higher than that of the bulk water at room temperature. The temperature derivative of the density shows a pronounced peak at T(L) = 235 K signaling the crossing of the Widom line at ambient pressure and confirming the existence of a liquid-liquid phase transition at an elevated pressure. Pore size and hydration level dependences of the density are also studied.     

Confined water inside single-walled carbon nanotubes: global phase diagram and effect of finite length

Studies on confined water are important not only from the viewpoint of scientific interest but also for the development of new nanoscale devices. In this work, we aimed to clarify the properties of confined water in the cylindrical pores of single-walled carbon nanotubes (SWCNTs) that had diameters in the range of 1.46 to 2.40 nm. A combination of x-ray diffraction (XRD), nuclear magnetic resonance, and electrical resistance measurements revealed that water inside SWCNTs with diameters between 1.68 and 2.40 nm undergoes a wet-dry type transition with the lowering of temperature; below the transition temperature T(wd), water was ejected from the SWCNTs. T(wd) increased with increasing SWCNT diameter D. For the SWCNTs with D = 1.68, 2.00, 2.18, and 2.40 nm, T(wd) obtained by the XRD measurements were 218, 225, 236, and 237 K, respectively. We performed a systematic study on finite length SWCNT systems using classical molecular dynamics calculations to clarify the effect of open ends of the SWCNTs and water content on the water structure. It was found that ice structures that were formed at low temperatures were strongly affected by the bore diameter, a = D - σ(OC), where σ(OC) is gap distance between the SWCNT and oxygen atom in water, and the number of water molecules in the system. In small pores (a < 1.02 nm), tubule ices or the so-called ice nanotubes (ice NTs) were formed irrespective of the water content. On the other hand, in larger pores (a > 1.10 nm) with small water content, filled water clusters were formed leaving some empty space in the SWCNT pore, which grew to fill the pore with increasing water content. For pores with sizes in between these two regimes (1.02 < a < 1.10 nm), tubule ice also appeared with small water content and grew with increasing water content. However, once the tubule ice filled the entire SWCNT pore, further increase in the water content resulted in encapsulation of the additional water molecules inside the tubule ice. Corresponding XRD measurements on SWCNTs with a mean diameter of 1.46 nm strongly suggested the presence of such a filled structure.     

Inorganic salt hydrates as cryoporometric probe materials to obtain pore size distribution

The depression of the melting temperature of Zn(NO3)2.6H2O was used to obtain the pore size distributions in controlled pore glasses. Measured by 1H NMR, the average value of the temperature depression DeltaT and the known average pore size yield K=DeltaT.d approximately 116 K.nm as the material-dependent factor for Zn(NO3)2.6H2O in the Gibbs-Thompson equation. The melting temperature is close to room temperature. Hence, this salt hydrate and some related other ones are better materials than water (K approximately 50 K.nm) for cryoporometric studies of systems with hydrophilic pores. The data also provide 46 mN/m for the solid-liquid surface tension of this salt hydrate.     

Mechanism of freezing of water in contact with mesoporous silicas MCM-41, SBA-15 and SBA-16: role of boundary water of pore outlets in freezing

The freezing mechanism of water contacted with mesoporous silicas with uniform pore shapes, both cylindrical and cagelike, was studied by thermodynamic and structural analyses with differential scanning calorimetry (DSC) and X-ray diffraction (XRD) together with adsorption measurements. In the DSC data extra exothermic peaks were found at around 230 K for water confined in SBA-15, in addition to that due to the freezing of pore water. These peaks are most likely to be ascribed to the freezing of water present over the micropore and/or mesopore outlets of coronas in SBA-15. Freezing of water confined in SBA-16 was systematically analysed by DSC with changing the pore size. The freezing temperature was found to be around 232 K, close to the homogeneous nucleation temperature of bulk water, independent of the pore size when the pore diameter (d) < 7.0 nm. Water confined in the cagelike pores of SBA-16 is probably surrounded by a water layer (boundary water) at the outlets of channels to interconnect the pores and of fine corona-like pores, which is similar to that present at the outlet of cylindrical pores in MCM-41 and of cylindrical channels in SBA-15. The presence of the boundary water would be a key for water in SBA-16 to freeze at the homogeneous nucleation temperature. This phenomenon is similar to those well known for water droplets in oil and water droplets of clouds in the sky. The XRD data showed that the cubic ice I(c) was formed in SBA-16 as previously found in SBA-15 when d < 8.0 nm.     

Melting and freezing of water in cylindrical silica nanopores

Freezing and melting of H(2)O and D(2)O in the cylindrical pores of well-characterized MCM-41 silica materials (pore diameters from 2.5 to 4.4 nm) was studied by differential scanning calorimetry (DSC) and (1)H NMR cryoporometry. Well-resolved DSC melting and freezing peaks were obtained for pore diameters down to 3.0 nm, but not in 2.5 nm pores. The pore size dependence of the melting point depression DeltaT(m) can be represented by the Gibbs-Thomson equation when the existence of a layer of nonfreezing water at the pore walls is taken into account. The DSC measurements also show that the hysteresis connected with the phase transition, and the melting enthalpy of water in the pores, both vanish near a pore diameter D* approximately equal to 2.8 nm. It is concluded that D* represents a lower limit for first-order melting/freezing in the pores. The NMR spin echo measurements show that a transition from low to high mobility of water molecules takes place in all MCM-41 materials, including the one with 2.5 nm pores, but the transition revealed by NMR occurs at a higher temperature than indicated by the DSC melting peaks. The disagreement between the NMR and DSC transition temperatures becomes more pronounced as the pore size decreases. This is attributed to the fact that with decreasing pore size an increasing fraction of the water molecules is situated in the first and second molecular layers next to the pore wall, and these molecules have slower dynamics than the molecules in the core of the pore.     

Confinement effects on the glass transition of hydrogen bonded liquids

The glass transition behavior of glycerol and propylene glycol confined in nanoporous glass is investigated using differential scanning calorimetry. Both silanized and unsilanized porous glasses are used to confine the liquids with nominal pore sizes ranging from 2.5 to 7.5 nm, and the glass transition temperature (T(g)) and the limiting fictive temperature (T(f )') are measured on cooling and heating, respectively. The effect of pore fullness is also examined. We find that differences in T(g), DeltaC(p), and the enthalpy overshoot behavior observed on heating are significant between partially and completely filled pores for the case of the unsilanized controlled pore glasses (CPGs) but that the effect of pore fullness is insignificant for the silanized CPGs. In general, the behavior in the silanized CPGs is similar to the behavior in the completely filled unsilanized pores. For glycerol, this includes a small depression in T(f )' on the order of 5 K at 2.5 nm. For propylene glycol, similar behavior is found except that an additional glass transition is observed in both silanized and unsilanized systems approximately 30 K higher than the bulk and a slightly smaller depression on the order of 3 K at 2.5 nm is observed in the completely filled unsilanized pores and in partially and completely filled silanized pores. The results are compared to those in the literature, and the confinement effects are discussed.     

Neutron scattering study on dynamics of water molecules in MCM-41. 2. Determination of translational diffusion coefficient

Quasielastic neutron scattering (QENS) spectra of water-filled MCM-41 samples (pore diameters: 21.4 and 28.4 Angstrom) were measured over the temperature range 238-298 K and the momentum transfer range 0.31-0.99 A(-1) to investigate the dynamics of confined water molecules. The spectra, which consist mainly of contributions from the translational diffusion of water molecules, were analyzed by using the Lorentzian and the stretched exponential functions. Comparison of the fits indicated that the latter analysis is more reliable than the former one. The fraction of immobile water molecules located in the vicinity of the pore walls, which give an elastic component, was found to be 0.044-0.061 in both pores. The stretch exponent beta was determined as 0.66-0.80. It was shown that the translational diffusion of water molecules in the pores is decelerated by confinement and that the deceleration becomes marked with a decrease in pore size. The ratios of the translational diffusion coefficient D(T) of confined water to that of bulk water at room temperature were within a range of 0.47-0.63.     

Structure of methanol confined in MCM-41 investigated by large-angle X-ray scattering technique

Large-angle X-ray scattering (LAXS) measurements over a temperature range from 223 to 298 K have been made on methanol confined in mesoporous silica MCM-41 with two different pore diameters, 28 A (C14) and 21 A (C10), under both monolayer and capillary-condensed adsorption conditions. To compare the structure of methanol in the MCM-41 pores with that of bulk methanol, X-ray scattering intensities for bulk methanol in the same temperature range have also been measured. The radial distribution functions (RDFs) for the monolayer methanol samples showed that methanol molecules are strongly hydrogen bonded to the silanol groups on the MCM-41 surface, resulting in no significant change in the structure of adsorbed methanol with respect to the pore size and temperature. On the other hand, the RDFs for the capillary-condensed methanol samples showed that hydrogen-bonded chains of methanol molecules are formed in both pores. However, the distance and number of hydrogen bonds estimated from the RDFs suggested that hydrogen bonds between methanol molecules in the pores are significantly distorted or partly disrupted. It has been found that the hydrogen bonds are more distorted in the smaller pores of MCM-41. With decreasing temperature, however, the hydrogen-bonded chains of methanol in the pores were gradually ordered. A comparison of the present results on methanol in MCM-41 pores with those on water in the same pores revealed that the structural change with temperature is less significant for confined methanol than for confined water.     

胶溶法制备镧-钡共稳定氧化铝的性能

以硝酸为胶溶剂, 两种拟薄水铝石为前驱体, 用胶溶法制备了镧-钡共稳定的氧化铝. 采用X 射线衍射(XRD)、表面分析仪(BET)、氨气程序升温脱附(NH3-TPD)和NO2程序升温脱附(NO2-TPD)技术对所制备的镧改性和镧钡共改性氧化铝的结构特性和表面性能进行了表征. XRD结果表明, 改性氧化铝在1273 K焙烧后均以γ-Al2O3相存在. 当BaO添加量达到14%(w)时, 有少量BaCO3生成. BET结果表明, 在1273 K下焙烧5 h后, 5%(w)La2O3稳定的氧化铝(Ba-0)和5%La2O3与8%BaO共同稳定的氧化铝(Ba-8)均具有较大的比表面积, 各种氧化铝的吸附等温线表明它们的孔形状均为狭缝型孔和瓶型孔, 孔径分布曲线表明, 仅有样品Ba-8的孔径分布较宽, 孔径为6-10 nm, 其它三种样品的孔径均集中在10 nm; NH3-TPD结果表明, 随着氧化钡添加量的逐渐增多, 氧化铝表面的酸量、酸强度逐步减少. NO2-TPD结果表明, 添加BaO后载体对NO2的吸附量增多, 随着BaO含量的增多, 体相Ba(NO3)2增多. 由于样品Ba-8同时具有很好的织构性质、适中的表面酸量和酸强度分布及NO2吸附脱附能力, 使得以它为载体的催化剂具有最好的催化性能,丙烷的起燃温度和完全转化温度分别为526 K和593 K.     

Fast thermal desorption spectroscopy study of H/D isotopic exchange reaction in polycrystalline ice near its melting point

Using fast thermal desorption spectroscopy, a novel technique developed in our laboratory, we investigated the kinetics of HD isotopic exchange in 3 microm thick polycrystalline H2O ice films containing D2O layers at thicknesses ranging from 10 to 300 nm at a temperature of -2.0+/-1.5 degrees C. According to our results over the duration of a typical fast thermal desorption experiment (3-4 ms), the isotopic exchange is confined to a 50+/-10 nm wide reaction zone located at the boundary between polycrystalline H2O and D2O ice. Combining these data with a theoretical analysis of the diffusion in polycrystalline medium, we establish the range of possible values for water self-diffusion coefficients and the grain boundary widths characteristic of our ice samples. Our analysis shows that for the grain boundary width on the order of a few nanometers, the diffusivity of D2O along the grain boundaries must be at least two orders of magnitude lower than that in bulk water at the same temperature. Based on these results, we argue that, in the limit of low concentrations of impurities, polycrystalline ice does not undergo grain boundary premelting at temperatures up to -2 degrees C.     

Enhanced mobility and increased gas sorption capacity in thin film and nanoconduit confined polymers

Poly(tert butyl acrylate) (PTBA) is found to exhibit enhanced mobility when spun cast into thin films or impregnated into cylindrical anodic aluminum oxide (AAO) nanoscale pores. In a thin film configuration, the glass transition temperature of 20 nm thick PTBA is found to decrease almost 20 °C compared to the bulk. Consistent with this mobility increase, an increased volume fraction of interphase polymer leads to at least a 2.4 times viscosity reduction when PTBA is impregnated in 100 nm pores versus 200 nm pores. Such increases in mobility result in a 15‐fold increase in CO₂ permeability for an AAO confined geometry compared to a bulk film. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 434–441, 2010     

Rotational motion in liquid water is anisotropic: a nuclear magnetic resonance and molecular dynamics simulation study

Experimental NMR measurements of the deuterium and (17)O T(1) relaxation times in deuterium-enriched liquid water have been performed from 275 to 350 K. These relaxation times can yield rotational correlation times of appropriate molecule-fixed unit vectors if the quadrupole coupling constants and asymmetry parameters are known. We determine the latter from ab initio studies of water clusters and experimental chemical shift measurements. We find that the rotational correlation time for the OD bond vector in D(2)(16)O varies from 5.8 ps at 275 K to 0.86 ps at 350 K, and that the rotational correlation time for the out-of-plane vector of dilute D(2)(17)O in D(2)(16)O varies from 4.4 ps at 275 K to 0.64 ps at 350 K. These results indicate that the rotational motion of water is anisotropic. Molecular dynamics simulations of liquid water are in good agreement with these experiments at the higher temperatures, but the simulation results are considerably faster than experiment at the lower temperatures.     

Y2O3和Nd2O3介孔薄膜的制备与表征

以聚乙烯合丁烯-嵌-聚氧乙烯嵌段共聚物(PHB-PEO)作模板, 采用蒸发诱导自组装方法, 分别制备了Y2O3和Nd2O3介孔薄膜. 用小角、广角X射线衍射和透射电子显微镜对薄膜样品在不同的热处理阶段进行了表征. 结果表明, 所制备的Y2O3和Nd2O3薄膜样品呈现一种大孔径(平均孔径分别约为11.5和12.5 nm)、有序的立方扭曲球形孔排列、稳定于450 ℃并具有部分晶态孔壁结构的介孔薄膜材料.     

Monte Carlo simulation of polymer adsorption

We developed and employed the incremental gauge cell method to calculate the chemical potential (and thus free energies) of long, flexible homopolymer chains of Lennard-Jones beads with harmonic bonds. The free energy of these chains was calculated with respect to three external conditions: in the zero-density bulk limit, confined in a spherical pore with hard walls, and confined in a spherical pore with attractive pores, the latter case being an analog of adsorption. Using the incremental gauge cell method, we calculated the incremental chemical potential of free polymer chains before and after the globual-random coil transitions. We also found that chains confined in attractive pores exhibit behaviors typical of low temperature physisorption isotherms, such as layering followed by capillary condensation.     

Ordered mesoporous silica with large cage-like pores: structural identification and pore connectivity design by controlling the synthesis temperature and time

FDU-1 silicas with large cage-like pores (diameter about 10 nm) were synthesized under acidic conditions from tetraethyl orthosilicate in the presence of a poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide) triblock copolymer template B50-6600 (EO(39)BO(47)EO(39)). High-resolution transmission electron microscopy and small-angle X-ray scattering provided strong evidence that FDU-1 silica synthesized under typical conditions is a face-centered cubic Fm3m structure with 3-dimensional hexagonal intergrowth and is not a body-centered cubic Im3m structure, as originally reported. Samples synthesized in a wide range of conditions (initial temperatures from 298 to 353 K; hydrothermal treatment at 333-393 K) exhibited similar XRD patterns and their nitrogen adsorption isotherms indicated a good-quality cage-like pore structure. The examination of low-pressure nitrogen adsorption isotherms for FDU-1 samples, whose pore entrance diameters were evaluated using an independent method, allowed us to conclude that low-pressure adsorption was appreciably stronger for samples with smaller pore entrance sizes. This prompted us to examine low-pressure adsorption isotherms for a wide range of samples and led us to a conclusion that the FDU-1 pore entrance size can be systematically enlarged from about 1.3 nm (perhaps even lower) to at least 2.4 nm without an appreciable loss of uniformity by increasing the temperature of the hydrothermal treatment or the initial synthesis. Further enlargement of pore entrance size was achieved for sufficiently long hydrothermal treatment times at temperatures of 373 K or higher, as seen from the shape of nitrogen desorption isotherms. This allowed us to obtain samples with uniform pore sizes, high adsorption capacity, and with pore entrances enlarged so much that their size was similar to the size of the pore itself, resulting in a highly open porous structure. However, in the latter case, there was evidence that the pore entrance size distribution was quite broad.     

Thermodynamic functions of water and ice confined to 2 nm radius pores

The heat capacity C(p) of the liquid state of water confined to 2 nm radius pores in Vycor glass was measured by temperature modulation calorimetry in the temperature range of 253-360 K, with an accuracy of 0.5%. On nanoconfinement, C(p) of water increases, and the broad minimum in the C(p) against T plot shifts to higher temperature. The increase in the C(p) of water is attributed to an increase in the phonon and configurational contributions. The apparent heat capacity of the liquid and partially frozen state of confined water was measured by temperature scanning calorimetry in the range of 240-280 K with an accuracy of 2%, both on cooling or heating at 6 K h(-1) rate. The enthalpy, entropy, and free energy of nanoconfined liquid water have been determined. The apparent heat capacity remains higher than that of bulk ice at 240 K and it is concluded that freezing is incomplete at 240 K. This is attributed to the intergranular-water-ice equilibrium in the pores. The nanoconfined sample melts over a 240-268 K range. For 9.6 wt % nanoconfined water concentration ( approximately 50% of the maximum filling) at 280 K, the enthalpy of water is 81.6% of the bulk water value and the entropy is 88.5%. For 21.1 wt % (100% filling) the corresponding values are 90.7% and 95.0%. The enthalpy decrease on nanoconfinement is a reflection of the change in the H-bonded structure of water. The use of the Gibbs-Thomson equation for analyzing the data has been discussed and it is found that a distribution of pore size does not entirely explain our results.     

孔结构对活性炭吸附水溶液中铅离子的影响

选取三种表面化学性质相近的活性炭(AC),通过等温吸附实验考察活性炭对水溶液中铅离子的吸附性能,利用扫描电子显微镜(SEM)观察活性炭的表面微观形貌,通过低温(77 K)液氮吸附测定活性炭的比表面积和孔容,并分别以密度泛函理论(DFT)和Barrett-Joyner-Halenda (BJH)法计算微孔和中孔的孔径分布.结果表明:选用的三种活性炭AC1、AC2、AC3在比表面积和总孔容上呈依次下降的趋势,但表面开放孔均匀分布的AC2,具有最高的饱和吸附量,孔结构类似颗粒堆积孔的AC3,具有与表面开放孔分布集中的AC1相近的饱和吸附量;通过对孔结构与吸附量的关联分析可知,在活性炭吸附铅离子的过程中, 0.4-0.6 nm的孔是有效吸附孔, 10.5-20.6 nm、20.6-55.6 nm、5.2-10.5 nm三个区间的孔则会对吸附产生阻碍作用.