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.     

Highly-controlled grafting of mono and dicationic 4,4'-bipyridine derivatives on SBA-15 for potential application as adsorbent of CuCl(2) from ethanol solution

Ultra-large-pore FDU-12 (ULP-FDU-12) silica with face-centered cubic structure (Fm3m type) of spherical mesopores was synthesized using Pluronic F127 triblock copolymer (EO(106)PO(70)EO(106)) and ethylbenzene as a new micelle expander at initial temperature of 14 °C. Ethylbenzene was identified on the basis of its reported extent of solubilization in poly(ethylene oxide)-poly(propylene oxide)-type surfactant micelles, which was similar to that of xylene, the latter having been shown earlier to afford ULP-FDU-12. The unit-cell parameter of as-synthesized ULP-FDU-12 was 55 nm, which is similar to the highest value reported when xylenes (mixture of isomers) were used and larger than that achieved with trimethylbenzene. The unit-cell parameter of calcined ULP-FDU-12 reached 52 nm. For the obtained materials, the nominal pore cage diameter calculated from nitrogen adsorption reached 32 nm, whereas the actual pore cage diameter calculated using the geometrical relation was 36 nm. The pore entrance size was below 5 nm before the acid treatment, but was greatly enlarged as a result of the treatment. The sample prepared without hydrothermal treatment was converted to ordered closed-pore silica at as low as 400-450 °C. Our study confirms the ability to select micelle expanders on the basis of data on solubilization of compounds in micelle solutions.     

Pore size tailoring in large-pore SBA-15 silica synthesized in the presence of hexane

Large-pore SBA-15 silicas were synthesized using poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer Pluronic P123 as a template and hexane as a micelle expander. The reaction was initially carried out at 15 degrees C, followed by the heating of the synthesis gel at temperatures from 40 to 130 degrees C. Small-angle X-ray scattering data indicate that highly ordered two-dimensional hexagonal material (SBA-15 structure) formed at 15 degrees C and was preserved even after 5 days of heating at 130 degrees C. The unit-cell parameter for as-synthesized SBA-15 silicas was about 16.5 nm and increased only slightly after the heat treatment, whereas the unit-cell parameter after calcination was appreciably larger (16 vs 14 nm) for materials that were subjected to the thermal treatment. The pore size distribution of SBA-15 formed at 15 degrees C was narrow and centered at approximately 9.5 nm, which is close to the upper limit of pore diameters typically reported for SBA-15. The presence of constrictions in the pores of this material was evident. The heat treatment led to the elimination of the constrictions and to the pore diameter increase to 15 nm or more, tailored by the selection of appropriate treatment temperature and time. The pore size increase was the fastest during the first day of treatment, but it continued for at least 5 days. The pore size distribution broadened as the time of the treatment increased beyond 1 day. The pore size increase appears to be primarily related to the decrease in the degree of shrinkage during the calcination (removal of the template) and the decrease in the pore wall thickness.     

Improvement of the Derjaguin-Broekhoff-de Boer theory for the capillary condensation/evaporation of nitrogen in spherical cavities and its application for the pore size analysis of silicas with ordered cagelike mesopores

In a previous work, we proposed an improvement of the Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in open-ended cylindrical mesopores. In this paper, we report a further extension of this approach to the capillary condensation/evaporation of nitrogen in siliceous spherical cavities. The main idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the variation of the surface tension in spherical mesopores. In addition, the statistical film thickness (the so-called t-curve), which is evaluated accurately on the basis of adsorption isotherms measured for MCM-41 materials, is used instead of the originally proposed t-curve to take into account the excess chemical potential due to the surface forces. It is shown that the aforementioned modifications of the original DBdB theory that was refined by Ravikovitch and Neimark have significant implications for the pore size analysis of cagelike mesoporous silicas. To verify the proposed improvement of the DBdB pore size analysis (IDBdB), two series of FDU-1 samples, which are well-defined cagelike mesoporous materials (composed of siliceous spherical cavities interconnected by short necks), were used for the evaluation of the pore size distributions (PSDs). The correlation between the spinodal condensation point in the spherical pores predicted by the nonlocal density functional theory (NDFT) developed by Ravikovitch and Neimark and that predicted by the IDBdB theory is very good in the whole range of mesopores. This feature is mirrored to the realistic PSD characterized by the bimodal structure of pores computed from the IDBdB theory. As in the case of open-ended cylindrical pores, the improvement of the classical DBdB theory preserves its simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the average pore size by the NDFT and the powder X-ray diffraction method.     

Synthesis of large-pore SBA-15 silica using poly(ethylene oxide)-poly(methyl acrylate) diblock copolymers

Poly(ethylene oxide)-poly(methyl acrylate) diblock copolymers with narrow molecular weight distributions were synthesized using atom transfer radical polymerization. The copolymers were used as micellar templates for the synthesis of mesoporous silicas. The products were characterized using small-angle X-ray scattering, transmission electron microscopy (TEM) and nitrogen adsorption. The obtained silicas exhibited two-dimensional hexagonal structures of cylindrical mesopores, and thus can be classified as SBA-15 silicas. In some cases, the size of ordered domains was very small. The (100) interplanar spacings were 13–17 nm, depending on the size of the diblock copolymer used and on the synthesis conditions. Nitrogen adsorption showed that the silicas exhibited specific surface areas of 350–800 m² g⁻¹, pore volumes ∼1 cm³ g⁻¹, and narrow pore size distributions. The BJH (nominal) pore diameters were up to ∼20 nm, but actual diameters of cylindrical pores are expected to be somewhat smaller. In many cases, the mesopores exhibited constrictions.     

Improvement of the Kruk-Jaroniec-Sayari method for pore size analysis of ordered silicas with cylindrical mesopores

In this work, the X-ray diffraction structure modeling was employed for analysis of hexagonally ordered large-pore silicas, SBA-15, to determine their pore width independently of adsorption measurements. Nitrogen adsorption isotherms were used to evaluate the relative pressure of capillary condensation in cylindrical mesopores of these materials. This approach allowed us to extend the original Kruk-Jaroniec-Sayari (KJS) relation (Langmuir 1997, 13, 6267) between the pore width and capillary condensation pressure up to 10 nm instead of previously established range from 2 to 6.5 nm for a series of MCM-41 and to improve the KJS pore size analysis of large pore silicas.     

The proper structure of cubic ice confined in mesopores

To examine the reason for the formation and the structure of cubic ice in a restricted space, we measured the powder x-ray diffraction patterns of cubic ice formed within the mesopores of porous silicas as a function of pore size (4-70 nm). The results strongly suggest that cubic ice formed in the mesopores does not take a cubic structure as envisaged by Konig. It may be actually composed of very small crystallites of hexagonal ice that contains a large amount of growth faults depending on the crystallite size, that is, ice with disordered stacking sequence. Suppression of crystal growth of ice in the mesopores seems to be a vital factor for the formation and the stability of cubic ice.     

Ordered mesoporous silicas and carbons with large accessible pores templated from amphiphilic diblock copolymer poly(ethylene oxide)-b-polystyrene

Highly ordered mesoporous carbons and silicas with ultralarge accessible pores have been successfully synthesized by using laboratory-made poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymers as templates via the evaporation-induced self-assembly (EISA) approach. Resols and tetraethyl orthosilicate (TEOS) serve as carbon and silica precursors, respectively. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) measurements show that the mesoporous carbons (denoted as C-FDU-18) possess face centered cubic closed-packing (fcc) mesostructure (Fm3m) with large-domain ordering. N2 sorption isotherms reveal a large mesopore at the mean value of 22.6 nm with a narrow pore-size distribution. Mesoporous silicas (Si-FDU-18) also display a highly ordered fcc closed-packing mesostructure with an ultralarge unit cell (a = 54.6 nm). A hydrothermal recrystallization was introduced for the first time to produce micropores in thick silica walls (approximately 7.7 nm) and thus to generate ultralarge accessible mesopores (30.8 nm). Notably, the amphiphilic diblock copolymer with high molecular weight (PEO125-PS230, 29700 g mol-1) in this report was prepared via a simple method of atom transfer radical polymerization (ATRP). It can be easily available for chemists even without any experience in polymer synthesis.     

Adsorption properties of ordered mesoporous silicas synthesized in the presence of block copolymer Pluronic F127 under microwave irradiation

Ordered mesoporous silicas (OMSs) were prepared at different temperatures by using tetraethyl orthosilicate (TEOS) as a silica source, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer (Pluronic F127) as a structure directing agent and sodium chloride as an additive under acidic conditions and microwave irradiation. The small angle X-ray diffraction patterns of these samples indicate the presence of ordered mesopores, while adsorption studies show that they possess high volumes of pores, bimodal pore size distributions and large pore sizes. There is an interesting change in the hysteresis loop of nitrogen adsorption isotherms with increasing temperature of hydrothermal treatment; a delayed desorption characteristic for cage-like mesostructures is observed for the OMS samples treated at 100 and 120?°C, while the hydrothermal treatment at 140 and 160?°C leads to the samples having hysteresis loops characteristic for channel-like materials.     

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.     

Nano-architectural silica thin films with two-dimensionally connected cagelike pores synthesized from vapor phase

Novel mesostructured silica thin films were prepared on a Si substrate by a vapor-phase synthesis. Vapor of tetraethoxysilane (TEOS) was infiltrated into a surfactant film consisting of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer. Nanophase transition from a lamellar structure to a two-dimensional cage structure of a silica-surfactant nanocomposite was found under vapor infiltration. The rearrangement into the cage structure implies high mobility of the silica-surfactant composites in solid phase. The silica thin films have two-dimensionally connected cagelike mesopores and are isotropic parallel to the film surface. The structure of pores of the films is advantageous for next-generation low-k films. The mesoporous structure has a large lattice parameter d of approximately 102 A, silica layer thickness of approximately 58 A, pillar diameter in the middle of approximately 60 A, pore size of approximately 72 A, BET surface area of approximately 729 m(2)/g, and pore volume of approximately 1.19 cm(3)/g. The films synthesized by the vapor infiltration show a lower concentration of residual Si-OH groups compared to the films prepared by a conventional sol-gel method. The films show high thermal stability up to 900 degrees C and high hydrothermal stability. This method is a simpler process than conventional sol-gel techniques and attractive for mass production of a variety of organic-inorganic composite materials and inorganic porous films.     

Grain size control of mesoporous silica and formation of bimodal pore structures

The architecture of mesoporous silica was successfully controlled by adjusting the concentrations of a cationic surfactant and ammonia. An excess amount of the surfactant suppressed the grain growth and then induced the formation of small grains with a diameter below 20 nm. Consequently, assembly of the small-sized grains produced a bimodal pore structure consisting of framework mesopores of 2-3 nm and textural mesopores ranging over 10-100 nm.     

Structural Control of Mesoporous 1,4-Phenylene-silica Using the Mixture of CTAB/SDS

The morphology, pore architecture and crystallinity of the mesoporous 1,4‐phenylene‐silicas were controlled using the mixtures of cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS). When the SDS/CTAB molar ratio increased from 0 to 1.0, the morphology of the mesoporous 1,4‐phenylene‐silicas changed in a sequence of sphere, hexagonal short rod, worm‐like, bent flake and flower‐like structure; the pore architecture of them changed from a hexagonal arranged tubular structure to a lamellar one; and the organization of the smallest repeat units within the wall changed from a random structure to a crystalline structure. At the SDS/CTAB molar ratios of 0.3 and 0.5, 1,4‐phenylene‐silica nanofibers with lamellar mesopores outside and tubular pore channels inside were obtained. The lamellar mesopores should be formed by merging the rod‐like micelles during the reaction process.     

Synthesis of ordered mesoporous NiO with crystalline walls and a bimodal pore size distribution

A mesoporous solid with crystalline walls and an ordered pore structure exhibiting a bimodal pore size distribution (3.3 and 11 nm diameter pores) has been synthesized. Previous attempts to synthesize solids with large ordered mesopores by hard templating focused on the preparation of templates with thick walls (the thick walls become the pores in the target materials), something that has proved difficult to achieve. Here the large pores (11 nm) do not depend on the synthesis of a template with thick walls but instead on controlling the microporous bridging between the two sets of mesopores in the KIT-6 template. Such control determines the relative proportion of the two pore sizes. The wall thickness of the 3D cubic NiO mesopore has also been varied. Preliminary magnetic characterization indicates the freezing of uncompensated moments or blocking of superparamagnetism.     

Controlling the shape and alignment of mesopores by confinement in colloidal crystals: designer pathways to silica monoliths with hierarchical porosity

Monolithic pieces of hierarchically structured silica, containing both periodic macropores and mesopores with well-controlled architecture, are synthesized by dual templating methods. Colloidal crystal templating with close-packed arrays of poly(methyl methacrylate) spheres yields regular, highly interconnected macropores a few hundred nanometers in diameter, and templating with nonionic surfactants produces mesoporosity (2.5-5.1 nm pore diameters) in the macropore walls. Several distinct mesostructures can be achieved within the silica skeleton, depending on the choice of surfactant, co-surfactant, and processing conditions. In the three-dimensional (3D) confinement of the colloidal crystal template, wormlike channels, cubic (Pm3n), or two-dimensional (2D) hexagonal (P6mm) mesostructures are produced with the surfactant Brij 56 (C16H33(OCH2CH2)nOH (n approximately 10) and dodecane as cosurfactant. In the 2D hexagonal structure, channels are oriented perpendicular to the polymer spheres, thereby connecting adjacent macropores through the silica walls. This orientation contrasts with channel alignment parallel to latex spheres when the polymeric surfactant Pluronic P123 (EO20PO70EO20) is used. On the basis of high-resolution 3D transmission electron microscopy, scanning electron microscopy, small-angle X-ray scattering, and nitrogen sorption measurements, structural and textural properties of the monoliths are described in detail as a function of the synthesis parameters. The control over the mesoarchitecture of these silica-surfactant systems in 3D confinement is explained by considering the relative dimensions of the mesostructures with respect to the interstitial space in the latex template, interfacial interactions, entropic effects, and structural frustration.     

Towerlike SBA-15: base and (10)-specific coalescence of a silicate-encased hexagonal mesophase tailored by nonionic triblock copolymers

Hydrothermal templating of mesoporous molecular sieves by nonionic triblock copolymers [poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) (PEO-PPO-PEO)] at specific block lengths of EO(20)PO(70)EO(20) and selected 2 M HCl dosage (pH -0.3) caused the formation of micrometer-sized SBA-15 hexagons with well-ordered hexagonal pore channels (pore size and wall thickness of approximately 6 nm and pore-to-pore distance of approximately 12 nm) after template removal. For a beneficial lower surface energy, these {10} laterally coalesced hexagons tend to stack imperfectly over the base into towerlike entities, leaving dislocations and faults within the single domain thus formed. Evidence for the mechanism of Brownian motion/coalescence of the hexagonal-mesophase particulates, previously suggested for MCM-41 accretion in the presence of cationic surfactant, is more clearly identifiable in the present low-pH case of amphiphilic block copolymer templates and linear silica oligomers.     

Ordered porous carbon with tailored pore size for electrochemical hydrogen storage application

Ordered porous carbon with tailored pore size represents an innovative concept in electrochemical hydrogen storage. This work deals with physical characteristics and electrochemical hydrogen storage behavior of the ordered porous carbons with well-tailored pore size, synthesized by a replica technique using hexagonal mesoporous silica as templates. By using a mixture of two surfactants (HTAB and C16EO8) at different ratios, it is possible to control the wall thickness of silica and, consequently, the pore diameter of carbons within a narrow range of 2.1-2.8 nm. In addition, highly developed ultramicroporosity (pore size smaller than 0.7 nm), which plays a predominant role in hydrogen storage, can be produced in the ordered porous carbons. A discharge capacity of up to 527 mAh/g (corresponding to 1.95 wt % hydrogen storage) has been achieved in 6 M KOH for the ordered porous carbon. Furthermore, the ordered porous carbons also possess excellent capacity retainability after charge-discharge cycles and rate capability.     

In Situ Small‐Angle X‐ray Scattering Investigation of the Formation of Dual‐Mesoporous Materials

The formation of a 2D‐hexagonal (p6m) silica‐based hybrid dual‐mesoporous material is investigated in situ by using synchrotron time‐resolved small‐angle X‐ray scattering (SAXS). The material is synthesized from a mixed micellar solution of a nonionic fluorinated surfactant, R^F₈(EO)₉ (EO=ethylene oxide) and a nonionic triblock copolymer, P123. Both mesoporous networks, with pore dimensions of 3.3 and 8.5 nm respectively, are observed by nitrogen sorption, transmission electron microscopy (TEM), and SAXS. The in situ SAXS experiments reveal that mesophase formation occurs in two steps. First the nucleation and growth of a primary 2D‐hexagonal network (N1), associated with mixed micelles containing P123, then subsequent formation of a second network (N2), associated with micelles of pure R^F₈(EO)₉. The data obtained from SAXS and TEM suggest that the N1 network is used as a nucleation center for the formation of the N2 network, which would result in the formation of a grain with two mesopore sizes. Understanding the mechanism of the formation of such materials is an important step towards the synthesis of more‐complex materials by fine tuning the porosity.     

Synthesis of ordered and disordered silicas with uniform pores on the border between micropore and mesopore regions using short double-chain surfactants.

Silica molecular sieves with uniform pores on the borderline between micropore (diameter <2 nm) and mesopore (from 2 to 50 nm) ranges were synthesized by a novel method using judiciously chosen mixtures of short double-chain alkylammonium surfactants. These silicas were characterized using X-ray diffraction (XRD), thermogravimetry, and nitrogen and argon adsorption. The calcined materials exhibited either 2-dimensional (2-D) hexagonal or disordered structures with XRD interplanar spacing from 2.51 to 2.93 nm, including the value of as small as 2.69 nm for highly ordered 2-D hexagonal silica. The dependence of the pore size and surfactant content on the surfactant chain length provided strong evidence for supramolecular templating being operative in the formation of small-pore silicas, even for the surfactant chain length of six carbon atoms. Both hexagonally ordered and disordered calcined samples were shown to exhibit narrow pore size distributions with maxima in the range from 1.96 to 2.61 nm (reliably evaluated on the basis of the unit-cell dimension and pore volume for 2-D hexagonal materials, and calculated using a properly calibrated procedure), tailored by the surfactant chain length. The samples exhibited primary pore volumes from 0.28 to 0.54 cm(3) g(-1) and specific surface areas from 730 to 930 m(2) g(-1). Because of their small yet uniform pore size and large specific surface area, the silicas reported herein promise to be useful in applications in adsorption and catalysis. Adsorption studies of these materials provided a unique new insight into the pore-filling mechanism for small-pore materials. Moreover, the approach proposed herein is expected to facilitate the synthesis of not only small-pore silicas but also materials with other framework compositions, thus largely contributing to bridging the gap in attainable pore sizes between micropore and mesopore ranges.     

Adsorption hysteresis of nitrogen and argon in pore networks and characterization of novel micro- and mesoporous silicas

We report results of nitrogen and argon adsorption experiments performed at 77.4 and 87.3 K on novel micro/mesoporous silica materials with morphologically different networks of mesopores embedded into microporous matrixes: SE3030 silica with worm-like cylindrical channels of mode diameter of approximately 95 angstroms, KLE silica with cage-like spheroidal pores of ca. 140 angstroms, KLE/IL silica with spheroidal pores of approximately 140 angstroms connected by cylindrical channels of approximately 26 angstroms, and, also for a comparison, on Vycor glass with a disordered network of pores of mode diameter of approximately 70 angstroms. We show that the type of hysteresis loop formed by adsorption/desorption isotherms is determined by different mechanisms of condensation and evaporation and depends upon the shape and size of pores. We demonstrate that adsorption experiments performed with different adsorptives allow for detecting and separating the effects of pore blocking/percolation and cavitation in the course of evaporation. The results confirm that cavitation-controlled evaporation occurs in ink-bottle pores with the neck size smaller than a certain critical value. In this case, the pressure of evaporation does not depend upon the neck size. In pores with larger necks, percolation-controlled evaporation occurs, as observed for nitrogen (at 77.4 K) and argon (at 87.3 K) on porous Vycor glass. We elaborate a novel hybrid nonlocal density functional theory (NLDFT) method for calculations of pore size distributions from adsorption isotherms in the entire range of micro- and mesopores. The NLDFT method, applied to the adsorption branch of the isotherm, takes into account the effect of delayed capillary condensation in pores of different geometries. The pore size data obtained by the NLDFT method for SE3030, KLE, and KLE/IL silicas agree with the data of SANS/SAXS techniques.