Synthesis of mesoporous silica materials with ascorbic acid as template via sol-gel process

Mesoporous silica materials with pore diameters of 2-5 nm have been prepared using ascorbic acid as a nonsurfactant template or pore-forming agent in HCl-catalyzed sol-gel reactions of tetraethylorthosilicate,followed by removing the ascorbic acid compound by extraction with ethanol.Characterization results from nitrogen sorption isotherm,powder X-ray diffraction and transmission electron microscopy indicate that the materials have large specific surface areas (e.g.1000 m2/g) and pore volumes (e.g.0.8 cm3/g).The rnesoporosity is arisen from interconnecting disordered wormlike channels and pores with relatively broad size distributions.As the ascorbic acid concentration is increased,the pore diameters and pore volumes of the materials increase.     

催化剂对乳液模板法制备碳材料形貌的影响

以液体石蜡为油相,间苯二酚和甲醛的水溶液为水相,吐温80和司班80为乳化剂,获得油/水(O/W)型乳状液.将该乳状液聚合、碳化去除模板后制得了碳材料,研究了不同催化剂对所得碳材料形貌的影响.结果表明:选择NaOH为催化剂时,制得的碳材料是一种具有孔壁和孔洞的多孔碳泡沫,典型样品的孔径约为1-2μm;当氨水为催化剂时,所得碳材料是由微球或者相互缠绕的蠕虫状粒子组成的块体材料,这些微球或粒子的直径主要集中在1-2μm,与NaOH为催化剂时所得碳泡沫的孔径尺寸相当.研究发现,氨水的加入使得乳液体系发生了相转化,由原来的O/W型乳液逐渐转变为W/O型高内相乳液.从分子间氢键出发,应用内聚能理论探讨了催化剂导致的乳液相变以及不同形貌碳材料的形成过程.     

Solvation force, structure and thermodynamics of fluids confined in geometrically rough pores

The effect of periodic surface roughness on the behavior of confined soft sphere fluids is investigated using grand canonical Monte Carlo simulations. Rough pores are constructed by taking the prototypical slit-shaped pore and introducing unidirectional sinusoidal undulations on one wall. For the above geometry our study reveals that the solvation force response can be phase shifted in a controlled manner by varying the amplitude of roughness. At a fixed amplitude of roughness, a, the solvation force for pores with structured walls was relatively insensitive to the wavelength of the undulation, lambda for 2.3/=0.5. The predictions of the superposition approximation, where the solvation force response for the rough pores is deduced from the solvation force response of the slit-shaped pores, was in excellent agreement with simulation results for the structured pores and for lambda/sigma(ff)>/=7 in the case of smooth walled pores. Grand potential computations illustrate that interactions between the walls of the pore can alter the pore width corresponding to the thermodynamically stable state, with wall-wall interactions playing an important role at smaller pore widths and higher amplitudes of roughness.     

Controlling optical properties and interchain interactions in semiconducting polymers by encapsulation in periodic nanoporous silicas with different pore sizes

The photophysics of MEH-PPV incorporated into the pores of periodic silica hosts has been investigated in an effort to understand the role played by interchain aggregation and chain morphology in polaron production. In this work, guest/host interactions were used to incorporate MEH-PPV into the straight, homogeneous pores of hexagonal surfactant- or polymer-templated mesoporous silicas of varying pore diameters. Polarized photoluminescence and photoluminescence excitation spectroscopy were then used to investigate the polymers' environment within the silica pores. Experiments exploiting luminescence peak shifts and depolarization indicate that depending on the pore size and preparation conditions, the alignment and packing of the polymer chains within the pores could be controlled. Samples could be produced with isolated chains, interacting straight chains, and coiled interacting chains. The sub-bandgap absorption by polarons was then measured with photoinduced absorption as a function of pore size. Small-diameter pores that allowed single polymer chains to reside within the pore showed little evidence of interchain contact and had a low polaron yield. Increasing the number of polymer chains within the pore increased the polaron yield. Finally, when the pores were large enough that the chains could coil, strong polaron absorption was observed, indicative of a further increase in polaron yield or an increase in polaron lifetime. The polaron absorption spectra also sharpen and red shift with increasing pore diameter, suggesting that excitons may migrate to lower energy polymer segments in samples where polymer chains are both coiled and interacting.     

Sorption kinetics of strontium in porous hydrous ferric oxide aggregates I. The Donnan diffusion model

Sorption of ions by hydrous ferric oxide (HFO) often shows a fast initial sorption reaction followed by a much slower sorption process. The second step is diffusion-controlled and can continue for days or months before equilibrium is reached. In this paper, we demonstrate that the diffusion rate may be explained by electrostatic interactions. The internal and external surfaces of HFO are generally positively charged and therefore repel cations. This can result in extremely low cation concentrations in pores, and therefore a significant reduction in pore diffusion rate. The theory is demonstrated here for sorption of Sr(2+) in HFO aggregates. The ion concentrations in the pore space are calculated using a Donnan model and diffusion is calculated from the Donnan concentration and potential gradients. This diffusion model is compared with nonelectrostatic pore diffusion, which does not take electrostatic interactions into account. The Donnan model predicts very low concentrations of Sr(2+) in the pores and diffusion rates that are up to 8000 times lower than predicted with a nonelectrostatic model.     

Packing effects on argon and methanol adsorption inside graphitic cylindrical and slit pores: a GCMC simulation study

Using Grand Canonical Monte Carlo simulation, we have studied the effects of confinement on argon and methanol adsorption in graphitic cylindrical and slit pores. Linear chain, zigzag and incomplete helical packing are observed for argon adsorption in cylindrical pores. However, for methanol adsorption different features appear because the electrostatic interactions favour configurations that maximize the hydrogen bonding among methanol molecules. We have found zigzag chains with hydrogen-bonded structures for methanol adsorption in cylindrical and slit pores. To investigate how dense the adsorbed phase is and how many molecules could be packed per unit physical volume of the solid, we consider two different definitions of pore density; one based on the physical volume and the other on the accessible volume. That based on accessible volume gives a measure of the fluid density, while that based on the physical volume gives a measure of how much adsorbate can be stored per unit volume of the adsorbent. It is found that the adsorbate is denser in cylindrical pores, but that slit pores can pack more molecules per unit solid volume. We also discuss the effects on the isosteric heat of argon and methanol of pore size, pore geometry and loading.     

Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)3.9H2O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time.     

Excluded volume effects in macromolecular forces and ion-interface interactions

A charged Yukawa liquid confined in a slit nanopore is studied in order to understand excluded volume effects in the interaction force between the pore walls. A previously developed self-consistent scheme [S. Buyukdagli, C. V. Achim, and T. Ala-Nissila, J. Stat. Mech. 2011, P05033] and a new simpler variational procedure that self-consistently couple image forces, surface charge induced electric field, and pore modified core interactions are used to this aim. For neutral pores, it is shown that with increasing pore size, the theory predicts a transition of the interplate pressure from an attractive to a strongly repulsive regime associated with an ionic packing state, an effect observed in previous Monte Carlo simulations for hard core charges. We also establish the mean-field theory of the model and show that for dielectrically homogeneous pores, the mean-field regime of the interaction between the walls corresponds to large pores of size d > 4 ?. The role of the range of core interactions in the ionic rejection and interplate pressure is thoroughly analyzed. We show that the physics of the system can be split into two screening regimes. The ionic packing effect takes place in the regime of moderately screened core interactions characterized with the bare screening parameter of the Yukawa potential b ? 3/l(B), where l(B) is the Bjerrum length. In the second regime of strongly screened core interactions b ? 3/l(B), solvation forces associated with these interactions positively contribute to the ionic rejection driven by electrostatic forces and enhance the magnitude of the attractive pressure. For weakly charged pores without a dielectric discontinuity, core interactions make a net repulsive contribution to the interplate force and also result in oscillatory pressure curves, whereas for intermediate surface charges, these interactions exclusively strengthen the external pressure, thereby reducing the magnitude of the net repulsive interplate force. The pronounced dependence of the interplate pressure and ionic partition coefficients on the magnitude and the range of core interactions indicates excluded volume effects as an important ion specificity and a non-negligible ingredient for the stability of macromolecules in electrolyte solutions.     

Interionic Interactions in Conducting Nanoconfinement

Interionic interactions in conducting nanopores determine how counterions may be packed in the pores subject to the applied voltage. In ideal metals, interactions are exponentially screened by metallic electrons. However, modern nanoporous electrodes are predominantly made of carbon materials. To what extent is this screening affected by a different mode of dielectric response in such materials? To answer this question we study Coulomb interaction of charges in cylindrical and slit pores that allow finite electric field penetration into the pore walls, as well as the Coulomb interaction in a nanogap between two thin walls of graphene modeled by a non‐local dielectric function. In all cases studied the screening was found to be subtly different than in metallic nanopores, but still strong enough to support realization of the so called superionic state in such pores.     

Biomimetic growth of silica tubes in confined media

Polymer membranes were used as biomimetic environments to study the effect of confinement on silica formation. Within membrane pores, silica tubes were formed, consisting of a dense silica shell incorporating nanoparticle aggregates. The shell structure does not depend on the membrane pore size, suggesting that its formation proceeds via interfacial interactions with the pore surface. In contrast, the size of primary nanoparticles within core aggregates is influenced by pore dimensions, indicating an effect of confinement on the diffusion-limited growth of silica. A parallel can be drawn with reported roles of confinement in biomineralization processes, providing a basis for future developments in biosilicification mimetic approaches and biofunctional nanomaterials design.     

Adsorption of DNA into mesoporous silica

In these experiments, double-stranded, linear DNA sequences were adsorbed into the pores of spherically shaped acid-prepared mesoporous silica (APMS). The lengths of the sequences were either 760 base pairs or 2000 base pairs. DNA adsorption into the interior of the mesoporous material was confirmed using confocal microscopy of sequences containing fluorescently labeled DNA molecules. Additional characterization with N(2) physisorption and powder X-ray diffraction supported this finding. The extent of adsorption was measured at various concentrations using UV-visible spectrophotometry to establish adsorption isotherms. APMS alone adsorbed a negligible amount of DNA; however, exchanging divalent cations such as Mg(2+) and Ca(2+) into the pores of APMS prior to DNA uptake was found to cause a significant amount of DNA to be adsorbed. Using Na(+) caused a lower amount of DNA to be adsorbed. DNA adsorption was also dependent on the pore diameter of APMS. Adsorption increased upon expansion of the pore size of the metal ion-exchanged material from 34 to 54 A; however, no additional uptake was measured by further increasing the pore size to 100 A. The amount of DNA adsorbed could also be significantly increased by using (aminopropyl)triethoxysilane to covalently link ammonium ions to the surface. Postsynthetic modification of the silica surface with aminopropyl groups increased the maximum DNA adsorption to 15.7 microg/mg silica, for materials with pore diameters of 100 A, which is 2 to 3 times more adsorbed DNA than for metal ion-exchanged material. This indicated that DNA binds more strongly in the presence of the ammonium group compared to the metal counterions. Finally, calculation and comparison of Freundlich and Langmuir constants for these adsorption processes indicate that intermolecular interactions between the DNA molecules within the pores are significant when the effective pore diameter is small, including materials with larger pores that were modified with organosilane.     

A superionic state in nano-porous double-layer capacitors: insights from Monte Carlo simulations

Recently observed anomalous properties of ionic-liquid-based nanoporous supercapacitors [C. Largot et al., J. Am. Chem. Soc., 2008, 130, 2730-2731] have attracted much attention. Here we present Monte Carlo simulations of a model ionic liquid in slit-like metallic nanopores. We show that exponential screening of the electrostatic interactions of ions inside a pore, as well as the image-charge attraction of ions to the pore surface, lead to the 'anomalous' increase of the capacitance with decreasing the pore width. The simulation results are in good agreement with the experimental data. The capacitance as a function of voltage is almost constant for low voltages and vanishes above a certain threshold voltage. For very narrow pores, these two regions are separated by a peak. With increase of the pore size the peak turns into a bump and disappears for wide pores. This effect, related to a specific character of the voltage-induced filling of nanopores with counterions at high densities, is yet to be verified experimentally.     

Characterization Studies on the Ionic Liquid-Templated Mesoporous Silica with Wormlike Pores

This article reports a novel preparation of wormlike mesoporous silica with 1-hexadecane-3-methylimidazolium bromide (C₁₆MIM)Br, a kind of room-temperature ionic liquids (RTILs), as a template via a sol-gel nanocasting technique. The characterization studies were carried out in contrast with that of the mesoporous silica with cetyltrimethylammonium bromide (CTAB), a usually used template, which has the same alkyl chain length with (C₁₆MIM)Br. The structures of the silica materials have been characterized by Transmission electron microscopy (TEM), High-resolution TEM (HRTEM) and N₂ adsorption-desorption measurements. The results show that both the mesoporous materials prepared with different templates respectively can form regular wormlike mesopores with ca. 2 nm in pore diameter. They also have large BET surface areas with narrow size distribution. Compared to the CTAB-template mesoporous silica, the material with (C₁₆MIM)Br as a template has highly uniform pore size and larger surface area. In addition, the formation mechanism of the wormlike mesopores with RTIL has been proposed by an electrostatic charge matching assembly-pathway and steric factor.     

Tractable molecular theory of transport of Lennard-Jones fluids in nanopores

We present here a tractable theory of transport of simple fluids in cylindrical nanopores, which is applicable over a wide range of densities and pore sizes. In the Henry law low-density region the theory considers the trajectories of molecules oscillating between diffuse wall collisions, while at higher densities beyond this region the contribution from viscous flow becomes significant and is included through our recent approach utilizing a local average density model. The model is validated by means of equilibrium as well nonequilibrium molecular dynamics simulations of supercritical methane transport in cylindrical silica pores over a wide range of temperature, density, and pore size. The model for the Henry law region is exact and found to yield an excellent match with simulations at all conditions, including the single-file region of very small pore size where it is shown to provide the density-independent collective transport coefficient. It is also shown that in the absence of dispersive interactions the model reduces to the classical Knudsen result, but in the presence of such interactions the latter model drastically overpredicts the transport coefficient. For larger micropores beyond the single-file region the transport coefficient is reduced at high density because of intermolecular interactions and hindrance to particle crossings leading to a large decrease in surface slip that is not well represented by the model. However, for mesopores the transport coefficient increases monotonically with density, over the range studied, and is very well predicted by the theory, though at very high density the contribution from surface slip is slightly overpredicted. It is also seen that the concept of activated diffusion, commonly associated with diffusion in small pores, is fundamentally invalid for smooth pores, and the apparent activation energy is not simply related to the minimum pore potential or the adsorption energy as generally assumed.     

Calculation of the adsorption-desorption hysteresis curves in narrow-pore systems

The gas and liquid spinodal branches for an adsorbate located in narrow slit-shaped, cylindrical, and spherocylindrical pores were calculated. The adsorbate is modeled by Lennard-Jones spherical particles. The calculation was based on the lattice gas model taking into account the intermolecular interactions of nearest neighbors in the quasichemical approximation. The density-temperature diagrams for the gas and liquid spinodal branches in the pores are similar to the equilibrium vapor-liquid phase diagrams: they have a common critical point; the dense-phase branches are shifted to lower pore fillings, while the rarefied-phase branches are shifted toward higher pore fillings. The width of adsorption-desorption hysteresis loop in the adsorption isotherms for Lennard-Jones particles was analyzed as a function of the pore size and the interaction potential of the adsorbate with the pore walls. The effect of pore wall roughness and the accuracy of isotherm calculation on the width of the adsorption-desorption hysteresis loop in cylindrical pores is discussed Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 813–823, May, 2007.     

Note on nonaqueous electrokinetic transport in charged porous media

A model for electrokinetic transport in charged capillaries is compared with experiments using nonaqueous lithium chloride solutions. The electrokinetic parameters considered are the pore fluid conductivity and the concentration potential. Methanol/water mixtures were the solvent, and track-etched mica membranes with a well-characterized pore structure were the porous medium. The electrolyte concentrations used were such that the Debye lengths of solutions in pores ranged from much smaller to much larger than the radius of pores. The space-charge model is found to be capable of qualitatively describing the trend of the electrokinetic data, but as expected, at higher concentrations the model fails, probably because the assumption that ion—ion interactions are negligible no longer holds. The experimental results show that the pore fluid conductivity depends strongly on the dielectric constant of the solvent, that the absolute value of the pore wall charge tends to decrease with the lowering of the solvent dielectric constant, and that the wall charge tends to increase with the concentration of the chloride ion.     

Facile synthesis of microporous carbon through a soft-template pathway and its performance in desulfurization and denitrogenation

Wormlike/lamellar microporous carbons were prepared by using long alkyl chain primary amine hydrochloride as the template and resorcinol/formaldehyde as the carbon source under highly acidic conditions. The template can be eliminated by high temperature treatment under an inert atmosphere. The obtained carbon materials were characterized by N2 adsorption-desorption, transmission electron microscopy, thermogravimetry and scanning electron microscopy. The results show that dodecylamine hydrochloride surfactant can be used as the template of wormlike micropores structure while octadecylamine hydrochloride results in both lamellar and wormlike micropores. The obtained carbon materials have the similar pore size in the range of 0.5~0.59 nm, but with various morphologies such as monolith, spheres, and coralline. The microporous carbon obtained from dodecylamine hydrochloride surfactant shows good adsorption performance to remove the refractory sulfur compounds and nitrogen-containing compounds in fuel.     

Screening of pi-basic naphthalene and anthracene amplifiers for pi-acidic synthetic pore sensors

Synthetic ion channels and pores attract current attention as multicomponent sensors in complex matrixes. This application requires the availability of reactive signal amplifiers that covalently capture analytes and drag them into the pore. pi-Basic 1,5-dialkoxynaphthalenes (1,5-DAN) are attractive amplifiers because aromatic electron donor-acceptor (AEDA) interactions account for their recognition within pi-acidic naphthalenediimide (NDI) rich synthetic pores. Focusing on amplifier design, we report here the synthesis of a complete collection of DAN and dialkoxyanthracene amplifiers, determine their oxidation potentials by cyclic voltammetry, and calculate their quadrupole moments. Blockage experiments reveal that subtle structural changes in regioisomeric DAN amplifiers can be registered within NDI pores. Frontier orbital overlap in AEDA complexes, oxidation potentials, and, to a lesser extent, quadrupole moments are shown to contribute to isomer recognition by synthetic pores. Particularly important with regard to practical applications of synthetic pores as multianalyte sensors, we further demonstrate that application of the lessons learned with DAN regioisomers to the expansion to dialkoxyanthracenes provides access to privileged amplifiers with submicromolar activity.     

Contact angles, pore condensation, and hysteresis: insights from a simple molecular model

We discuss the thermodynamics of adsorption of fluids in pores when the solid-fluid interactions lead to partial wetting of the pore walls, a situation encountered, for example, in water adsorption in porous carbons. Our discussion is based on calculations for a lattice gas model of a fluid in a slit pore treated via mean field density functional theory (MFDFT). We calculate contact angles for pore walls as a function of solid-fluid interaction parameter, alpha, in the model, using Young's equation and the interfacial tensions calculated in MFDFT. We consider adsorption and desorption in both infinite pores and in finite length pores in contact with the bulk. In the latter case, contact with the bulk can promote evaporation or condensation, thereby dramatically reducing the width of hysteresis loops. We show how the observed behavior changes with alpha. By using a value of alpha that yields a contact angle of about 85 degrees and maintaining the bulk fluid in a supersaturated vapor state on adsorption, we find an adsorption/desorption isotherm qualitatively similar to those for graphitized carbon black where pore condensation occurs at supersaturated bulk vapor states in the spaces between the primary particles of the adsorbent.     

Synthetic pores with sticky pi-clamps

In this report, we describe design, synthesis, evaluation and molecular dynamics simulations of synthetic multifunctional pores with pi-acidic naphthalenediimide clamps. Experimental evidence is provided for the formation of unstable but inert, heterogeneous and acid-insensitive dynamic tetrameric pores that are sensitive to base and ionic strength. Blockage experiments reveal that the introduction of aromatic electron donor-acceptor interactions provides access to the selective recognition of pi-basic intercalators within the pore. This breakthrough is important for the application of synthetic pores as multianalyte sensors.