Density profile of water confined in cylindrical pores in MCM-41 silica

Recently, water absorbed in the porous silica material MCM-41-S15 has been used to demonstrate an apparent fragile to strong dynamical crossover on cooling below ～220 K, and also to claim that the density of confined water reaches a minimum at a temperature around 200 K. Both of these behaviours are purported to arise from the crossing of a Widom line above a conjectured liquid-liquid critical point in bulk water. Here it is shown that traditional estimates of the pore diameter in this porous silica material (of order 15 ?) are too small to allow the amount of water that is observed to be absorbed by these materials (around 0.5 g H(2)O/g substrate) to be absorbed only inside the pore. Either the additional water is absorbed on the surface of the silica particles and outside the pores, or else the pores are larger than the traditional estimates. In addition the low Q Bragg intensities from a sample of MCM-41-S15 porous silica under different dry and wet conditions and with different hydrogen isotopes are simulated using a simple model of the water and silica density profile across the pore. It is found the best agreement of these intensities with experimental data is shown by assuming the much larger pore diameter of 25 ? (radius 12.5 ?). Qualitative agreement is found between these simulated density profiles and those found in recent empirical potential structure refinement simulations of the same data, even though the latter data did not specifically include the Bragg peaks in the structure refinement. It is shown that the change in the (100) peak intensity on cooling from 300 to 210 K, which previously has been ascribed to a change in density of the confined water on cooling, can equally be ascribed to a change in density profile at constant average density. It is further pointed out that, independent of whether the pore diameter really is as large as 25 ? or whether a significant amount of water is absorbed outside the pore, the earlier reports of a dynamic crossover in supercooled confined water could in fact be a crystallization transition in the larger pore or surface water.     

Phase transitions in KNO3 embedded in MCM-41 films with regular nanopores

This paper reports on a comparative study of phase transitions in nanocomposites made up of KNO₃ embedded in 10-μm-thick MCM-41 films with unidirectional pores 4.0 nm in size on an aluminum substrate and of nanocomposites prepared in the form of potassium-nitrate-filled pressed MCM-41 powders with 3.7-nm pores. The temperature dependences of linear permittivity and the amplitude of third harmonic generation have been measured under heating and cooling. The structural transition from phase II to phase I shifts under heating relative to that occurring in bulk KNO₃ toward lower temperatures for potassium nitrate in the film and toward higher temperatures for the pressed MCM-41-based nanocomposite. A significant difference has been observed also within the region of existence of ferroelectric phase III. The data obtained suggest that the shifts of phase transition temperatures observed in the conditions of nanoconfinement are influenced markedly not only by pore size and geometry but also by other factors.     

Dielectric properties of mixed NaNO2-KNO3 ferroelectrics in nanoporous silicate matrices

Physics of the Solid State - Results of dielectric studies of MCM-41 molecular sieves with mesoporous channels (37.0 and 24.3 Å in size) loaded with the ferroelectric (NaNO2)1 ? x (KNO3)...     

Dielectric properties of the nanoporous MCM-41 matrix filled with the (NH4)2SO4 ferroelectric

Variations with temperature of the linear dielectric permittivity and amplitude of the third harmonic were studied for nanoporous MCM-41 matrices with 4.0-nm channel pores filled with the (NH₄)₂SO₄ ferroelectric, in comparison with bulk ammonium sulfate. The measurements were performed upon heating and cooling in the temperature range from 100 K to room temperature. A noticeable shift to low temperatures (by approximately 25 K) for the ferroelectric phase transition in the MCM-41/(NH₄)₂SO₄ nanocomposite as compared to bulk (NH₄)₂SO₄ was revealed. The temperature hysteresis observed at the phase transition in the nanocomposite was approximately 2 K which is close to that in bulk ammonium sulfate. The significant decrease of the transition temperature in nanostructured ammonium sulfate agrees with the theoretical predictions based on the Landau and Ising models of the size effect on the ferroelectric phase transition in isolated small particles.     

Strong visible photoluminescence of TEEDPS-modified silica MCM-41 materials

The photoluminescence (PL) of mesoporous silica MCM-41 modified with triethoxy-3-ethylenediaminepropyl-silane (TEEDPS) has been investigated using UV-Vis fluorescence and absorption spectroscopy methods and thermogravimetry. Results suggest that the TEEDPS-modified MCM-41 has a greatly enhanced (by 20 times) PL intensity at 420 nm relative to that of TEEDPS, and this enhanced PL still remains even after post heat treatment at 180 °C under vacuum (yielding a sample MTV). Meanwhile, a strong PL band at 450 nm appeared in the sample MTV when excited at 380 nm. The TEEDPS-modified material could be partly oxidized at 180 °C in air (yielding a sample MTA); therefore obvious absorption was found up to about 600 nm. The interaction between this absorption and the vacancy-related emission resulted in the maximum of the emission bands of the sample MTA at around 515 nm when excited at 440 nm. PACS 78.55.Mb; 78.55.Hx; 79.60.Jv; 78.40.Ha     

Dielectric and NMR studies of nanoporous matrices loaded with sodium nitrite

NMR and dielectric studies have been performed on NaNO₂ loaded in mesoporous matrices of MCM-41 and SBA-15 with pore sizes of 20, 37, and 52 Å. The spin-lattice relaxation rate and ²³Na NMR line shape, as well as the complex impedance, were measured within a broad temperature interval including the ferroelectric phase transition in bulk NaNO₂. Two different phases of sodium nitrite, the crystalline and melt phases, are shown to coexist under conditions of a restricted geometry. The crystalline phase undergoes a ferroelectric phase transition. The melt fraction increases with temperature. The existence of two phases accounts for all experimental data on NaNO₂ under conditions of a restricted geometry.     

Dielectric and Polarization Studies of KNO3 Thin Layers

Ultrapure and homogeneous KNO₃ thin layers are subjected to dielectric and polarization measurements over a wide temperature range. The dielectric results obtained are discussed on the assumption of probable formation and migration of vacancies. The variation of polarization with the applied field was found to be nonlinear and the polarization reversal occurs at a critical value of the applied field of strength 11 kV/cm. This value is in good agreement with the value of the coercive field determined previously by the ferroelectric hysteresis loops.     

Cadmium sulphide clusters grown on zeolite and MCM-41-type matrices

Cadmium sulphide clusters were grown on mordenite and Al-MCM41 matrices by using hydrothermal synthesis. X-ray fluorescence and diffraction, Raman spectroscopy, N₂-adsorption isotherms, UV-visible and photoluminescence spectroscopies were used for sample characterisation. The results confirm the growth of CdS clusters mainly on the mordenite surface, whereas they could grow inside the mesoporous MCM-41 matrix. The final products showed approximately the same band-gap value (2.35 eV) as that calculated for bulk CdS synthesised in this work for comparison. Refractive indexes and extinction and absorption coefficients of the samples were evaluated by using a computational program. The mean values of those magnitudes and their connections with the structure, morphology and composition of the CdS-doped matrices were analysed. The relation between optical non-linearities and the growth of other species, like SiO_x, during the synthesis processes is also discussed. PACS 81.05.Dz; 81.40.Tv; 82.75.Vx     

Dielectric and Thermal Properties of KNO3 Encapsulated in Carbon Nanotubes

Physics of the Solid State - The results of the study of phase transitions of KNO3 encapsulated in carbon nanotubes are presented. It is shown that the temperature range of existence of KNO3...     

Adsorption of argon and nitrogen in cylindrical pores of MCM-41 materials: application of density functional theory

Adsorption of argon and nitrogen at their respective boiling points in cylindrical pores of MCM-41 type silica-like adsorbents is studied by means of a non-local density functional theory (NLDFT), which is modified to deal with amorphous solids. By matching the theoretical results of the pore filling pressure versus pore diameter against the experimental data, we arrive at a conclusion that the adsorption branch (rather than desorption) corresponds to the true thermodynamic equilibrium. If this is accepted, we derive the optimal values for the solid-fluid molecular parameters for the system amorphous silica-Ar and amorphous silica-N₂, and at the same time we could derive reliably the specific surface area of non-porous and mesoporous silica-like adsorbents, without a recourse to the BET method. This method is then logically extended to describe the local adsorption isotherms of argon and nitrogen in silica-like pores, which are then used as the bases (kernel) to determine the pore size distribution. We test this with a number of adsorption isotherms on the MCM-41 samples, and the results are quite realistic and in excellent agreement with the XRD results, justifying the approach adopted in this paper.     

Condensation process of alcohol molecules on mesoporous silica MCM-41 and SBA-15 and fumed silica: a spin-probe ESR study

A few alcoholic solutions of di-tert-butyl nitroxide (DTBN), a spin probe, at a high concentration were condensed on several silica materials, such as MCM-41, two types of SBA-15, and fumed silica, at various amounts in vacuum. At a very low solution dose the electron spin resonance (ESR) spectrum is that of an immobilized nitroxide radical. With increasing solution dose, the spectrum is gradually sharpened and a well-separated three-line spectrum is observed at the dose that is estimated to fill the surface with a monomolecular layer. Thus, the DTBN molecule can make rapid tumbling motion on this solvent layer. With a further increase in the solution dose the ESR spectrum is modified in different ways from system to system: the line width increases approximately linearly with respect to the solution dose for the SBA-15 and fumed silica systems, but it remains almost constant for the MCM-41 system until the solution dose exceeds the total volume of a nanochannel. The line width increase with respect to the solution dose is small for the SBA-15 system but large for the fumed silica system. These results have been interpreted geometrically with the structures of these silica materials and a condensation model for the alcohols on these surfaces. In relation to the present results, a model of the collective molecular flow of the alcohol solutions through the nanochannel of MCM-41 is given.     

Adsorptive removal of anionic dyes by modified nanoporous silica SBA-3

Batch sorption experiments were carried out to remove dyes, methyl orange (MO), orange G (OG) and brilliant red X-3B (X-3B), from their aqueous solutions using a mesoporous silica SBA-3 as an adsorbent. The effect of surfactant template in SBA-3 on the removal of OG, MO and X-3B was investigated. Experiments were carried out to investigate the influence of contact time, initial concentration, pH, and adsorbent dosage on the adsorption performance. The adsorption results of anionic dyes on the uncalcined SBA-3 (noted as SBA-3) were compared with those of the calcined SBA-3 (noted as C-SBA-3). The uncalcined SBA-3 adsorbent has a large adsorption capacity and a strong affinity for the anionic dyes. Langmuir, Freundlich and Temkin isotherms were employed to model the experimental results, from which the Freundlich isotherm exhibited the most appropriate to predict the same. Freundlich isotherm exhibited the most appropriate to predict the experimental results. The kinetic data were also analyzed through pseudo-first-order and pseudo-second-order models. The pseudo-second-order kinetic model well depicted the kinetics of dyes adsorption on mesoporous SBA-3.     

Dielectric investigations of solid solutions SrTiO3-KTaO3 and SrTiO3-KNbO3

The temperature dependences of the dielectric constant and dielectric hysteresis loops in ceramic samples of (1 ? x)SrTiO_3?x KNbO₃ and (1 ? x)SrTiO_3?x KTaO₃ (0 ≤ x ≤ 0.3) solid solutions prepared using different heat treatments have been investigated. Phase diagrams of the studied solid solutions have been constructed in the T-x coordinates. It has been shown that, after quenching of samples (spontaneous cooling at room temperature after long-term heating at the sintering temperature of the ceramic samples), the temperature of the induced phase transition increases because of the weakening of random electric fields associated with nonisovalent impurities due to their “frozen” nonequilibrium redistribution. For small concentrations x, strong dielectric relaxation is observed in the temperature range of 150–250 K. A model of relaxing centers, which is based on the local charge compensation of heterovalent impurities, has been proposed.     

Oxidation of ferrocene molecules adsorbed in MCM-41

A mesoporous silica material MCM-41 was synthesized under two different conditions, and ferrocene molecules were adsorbed into one-dimensional pores formed in MCM-41. The pore sizes were determined to be 0.9 and 2.8 nm for the MCM-41 synthesized under an acidic and a basic condition, respectively. The formation of paramagnetic ferricinium ions was observed after the adsorption into pores by ESR, magnetic susceptibility and ⁵⁷Fe Mössbauer measurements. Spin densities attributable to ferricinium ions in the pores are estimated to be 0.74 and 0.065 in MCM-41 synthesized under an acidic and a basic condition, respectively. It was shown that the oxidation of ferrocene molecules to ferricinium ions in MCM-41 prepared in an acid solution is faster than that in base at ambient temperature and pressure.     

Photonic band structure of 3D ordered silica matrices

The symmetry and orientation of a photonic lattice of 3D ordered porous silica matrices (synthetic opals) are determined by analysis of transmission electron micrographs. By optical transmission measurements the photonic band edges are mapped out at pointsLandKof the Brillouin zone. It is shown that modulating the refractive index of opal pores by filling them with liquids results in variation of the light attenuation length within the forbidden gap. To increase the refractive index contrast of the lattice, the pores of opals were filled with CdS. A dramatic decrease in attenuation length is observed for opal/CdS. The parameters of a photonic lattice with a ‘pseudo-gap’, that is, with a prominent depletion of the photonic density of states, are estimated.     

Dielectric and calorimetric behaviour of liquids systems containing halogenotoluenes

A study of the dielectric relaxation of the monohalogenotoluenes was carried out by measuring their dielectric constants at 2 MHz and complex dielectric permittivities at 9.23 and 15.05 GHz, in the range 293.15 – 323.15 K. The activation energies of the relaxation process, were obtained from Eyring and Bauer models at 303.15 K.On the other hand, the excess molar enthalpies of the equimolecular binary halogenotoluene + benzene mixtures, H^E_x=0.5, were determined and correlated with the activation energies of the pure polar components.     

Four pulse electron spin echo modulation studies of Cu(II) complexes in MCM-41 silica tube materials

The coordination geometry of Cu(II) complexes with water and ammonia has been studied by four pulse electron spin echo modulation spectroscopy in siliceous (L)Cu-MCM-41 and in aluminum-containing (L)Cu-AlMCM-41 where (L) denotes Cu(II) incorporation by liquid phase ionexchange. An analysis of the proton sum peaks in the echo modulation pattern of the water and ammonia ligands reveals significant differences in the Cu(II) coordination between MCM-41 and AlMCM-41. In the aluminum-containing material (L)Cu-AlMCM-41, Cu(II) coordinates to two molecules of water or ammonia and three framework oxygens in a square-based pyramidal coordination geometry. The base of the pyramid is formed by two adsorbate molecules together with two framework oxygens. A third framework oxygen is located at the apex of the pyramid. The cupric ion site is slightly shifted from the plane of the pyramid base towards the apex resulting in an off-plane position. In the siliceous material (L)Cu-MCM-41, [Cu(H₂O)₆]²⁺ and [Cu(NH₃)₄]²⁺ complexes are observed. The results of four pulse electron spin echo modulation experiments support a distorted octahedral coordination geometry for the [Cu(H₂O)₆]²⁺ complex in (L)Cu-MCM-41.     

Melting of Naphthalene Confined in Mesoporous Silica MCM-41

The ²H nuclear magnetic resonance (NMR) solid-echo spectra of naphthalene molecules as guests in the mesopores of neat MCM-41 with a pore width of 3.3 nm were measured in the temperature regime from 180 to 250 K. A strong reduction of the melting point of the naphthalene molecules by 152 K is observed. The line shape changes in the melting region were simulated with two different models, namely, the model of a narrow distribution of activation energies, which is typical for a crystal-like phase, and a two-phase model. Both models indicate a relatively narrow distribution of melting points of the naphthalene molecules inside the pores, indicative of a rather well-defined structure of the naphthalene molecules inside the pores. This finding supports the proposal of a plastic crystalline phase previously proposed by other groups.     

分子筛组装单质半导体碲的拉曼光谱

无机介孔材料MCM41是高有序,直孔道介孔分子筛,具有孔径约4nm的一维均匀孔道,孔壁厚约1nm,介孔体积可达40%,是一种很理想的组装材料主体。半导体碲位于第Ⅵ族,其六方相的晶格排列呈螺旋链状结构。本文采用固相合成反应方法,将单质半导体碲成功地组装在MCM41介孔分子筛中。在组装体中,单质半导体碲保持着六方相的晶体结构,其拉曼晶体振动表现出纳米晶体的结构特征。真空热处理实验表明,组装体具有良好的热稳定性。Te的六方相和所具有的独特的螺旋链状结构使Te分子很容易进入MCM41的直孔道内,同时MCM41均匀而规则的直孔道限制了Te螺旋链的随机排列,因而被组装在直孔道内的Te能螺旋链式生长,形成一维半导体纳米晶体,排列均匀,尺寸单一,具有稳定的空间构型     

Structure and dynamic properties of liquids confined in MCM-41 mesopores

The microscopic structure and dynamic properties of water, methanol, and acetonitrile confined in mesoporous MCM-41 materials have been investigated under monolayer and capillary-condensation conditions as a function of pore size and temperature by in situ FTIR and X-ray diffraction and quasi-elastic neutron scattering techniques. Both interfacial and confinement effects on the structure and dynamics of the liquids in hydrophilic pores are discussed at the molecular level.