Fractal approach to the CO oxidation on silica porous materials

We present an approach establishing a relation between the activation energy of heterogeneous catalytic processes and the fractal dimension of a catalyst. The approach is verified by experimental study of the CO oxidation on various porous silica and zeolite NaX. The fractal dimension of a catalyst (D_F) was calculated from the nitrogen adsorption isotherms. Our results indicate that the activation energy increases with increasing the fractal dimension of a catalyst. We show a good correspondence between theoretical and experimental results.     

Glucose diffusivity and porosity in silica hydrogel based on organofunctional silanes

The silica hydrogels prepared at physiological conditions were characterized with respect to the glucose diffusion properties and the porosity by employing various approaches. A diffusion coefficient of glucose in silica hydrogel in the range of 2 × 10⁻¹⁰ m² s⁻¹ was determined by two complementary techniques based on the glucose ingress and egress, respectively. The confocal laser scanning microscopy in a time-lapse imaging mode was employed to measure the ingress of fluorescently labeled glucose analogue inside the hydrogel. In addition, a method for direct glucose release from the hydrogel was established. The simple diffusion model based on the Fickian diffusion and Ritger–Peppas theory were employed for evaluation of diffusion coefficients, respectively. The BET analysis and permeation of fluorescently labeled dextrans of various molecular weights were used to characterize the porosity of silica hydrogel. The radius of pores accessible for diffusion of dextran molecules in prepared silica hydrogel ranges between 1 and 6 nm.     

Diffusion-based deprotection in mesoporous materials: a strategy for differential functionalization of porous silica particles

A monodisperse, spherical mesoporous silica (Acid-Prepared Mesoporous Spheres, APMS) was prepared and then functionalized with two types of Fmoc (9-fluorenylmethyloxycarbonyl) terminated silanes with variable chain lengths. N2 physisorption experiments indicated that, under some conditions, the pores of the solid were completely filled by the Fmoc-protected organosilanes. These blocked pores were then "reopened" by the cleavage of Fmoc groups with a piperidine solution. In contrast to the solution reaction, this deprotection reaction was much slower within the pores. The rate of deprotection was followed by UV/visible spectroscopy, and a plot of Fmoc released versus time showed a sigmoidal shape. An empirical model was applied to the data, which indicated that the reaction was influenced by the concentration and temperature of the piperidine solution as well as the number of Fmoc moieties within the pores. Using this information, we show that the location of the deprotection reaction in the pores of the silica can be empirically controlled. Our work provides a method by which the surface of the porous silica can be functionalized in a well-defined manner. This method can be used to produce materials for catalysis or drug delivery.     

Fractality of materials based on silica gel

Based on the analysis of the isotherms of N₂ adsorption, the fractal dimension and other texture geometric parameters were determined for silica gel, modified silica gel, and relevant composite materials. The correlations between the texture parameters were found. A criterion for the estimation of the efficiency of using the composite adsorbent volume was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 781–785, May, 2000.     

Novel architectures in porous materials based on clays

Modification of layered clays in view to develop porous materials, mainly for catalytic applications, has been afforded in the past via intercalation reaction of aluminum and other polyoxycations or through generation of mesoporous silica between the layers of the silicate. In this paper it is introduced examples of an alternative route for the preparation of porous nanoarchitectures based on the sol–gel method that profits from the swelling ability of organoclays in organic solvents to incorporate silicon and/or other metal (e.g., Ti, Al,…) alkoxides in the interlayer region of the silicates where they are hydrolyzed in a controlled manner. Their further polycondensation originates the formation of an oxide matrix and after a thermal treatment is possible the consolidation of oxide nanoparticles between delaminated smectites and vermiculites. It is also showed how this colloidal route can be applied to the generation of oxide nanoparticles bonded to the external surface of fibrous clays, such as sepiolite. Finally, it is also summarized with various examples the potential interest of the resulting porous clay nanoarchitecture materials in applications as acid catalysts, photocatalysts or nanofillers in polymer–clay nanocomposites.     

Surface‐dependent effect of functional silica fillers on photocuring kinetics of hydrogel materials

Two types of silica: precipitated (P, prepared in non‐polar media, a new type, submicrometer sized) and fumed (F, nanosized), both unmodified and surface modified are investigated as functional fillers for potential applications in nanocomposites with poly(2‐hydroxyethyl methacrylate) matrix. Special attention is paid to the kinetics of composite formation in an in situ photopolymerization process. Silica‐containing formulations polymerize faster; this effect is much stronger for silica P having much larger particle size than silica F. Surface treatment leads to further acceleration of the polymerization in case of silica P but to retardation in case of silica F; the effect of modification of the filler surface on properties of composites is different for each of the silicas. The obtained results are discussed in terms of effects of curvature of silica particles, surface properties, solvation cell, interphase region, viscosity changes, and morphology of the resulting composites. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3472–3487     

The transport of adsorbate mixtures in porous materials: Basic equations for pores with simple geometry

The basic equations governing the transport of single and binary adsorbate mixtures through single pores are considered. An irreversible thermodynamic formulation is adopted and both viscous and diffusive terms are incorporated following the earlier work of Mason and co-workers. The links between phenomenological coefficients and molecular properties are demonstrated. For single components, the gas phase and high density limits are considered. By using simple hydrodynamic models it is shown that the phenomenological coefficients in the mixture equations can all be expressed as functions of the coefficients for the individual components in the same pore, and the properties of the component adsorption isotherms. Whilst it is appreciated that the hydrodynamic approach will be of limited value in very small pores, it is argued that useful insights can be gained into the feasibility of membrane separation processes from this method. The general equations can be used in future development of network models for porous materials.     

A model for polybutadiene coatings on porous silica

Summary Non-wetting viscous liquids such as oligobutadiene prefer active sites such as pores during the process of physisorption. Thus, polybutadiene (PBD) coatings on porous silica do not result in a homogeneous polymer film but in an inhomogeneous loading where the bulk polymer is mainly sited in the pores of the silica. An increasing polymer loading leads to increasingly filled pores instead of a thicker polymer film. We cannot exclude the possibility that most of the surface is covered at least with a thin polymer film since the chromatographic behaviour is relatively good for polypeptides, which are highly susceptible to the silanol groups of silica.     

Stellate porous silica based surface-enhanced Raman scattering system for traceable gene delivery

Numerous nanocarriers have been currently developed for intracellular delivery. The potential cytotoxicity of these very small inorganic nanocarriers has raised great consideration. Thus, it becomes of utmost importance to conduct the intracellular trace of nanocarriers. Among many analytical techniques, surface enhanced Raman scattering(SERS) method is one of the current state-of-the-art techniques for cell visualization and trace. In this work, a novel stellate porous silica based gene delivery system has been designed for SERS trace purpose. A stellate porous silica nanoparticle modified with many small Au nanoparticles is designed to replace common metallic SERS tags. The results show that the designed system not only could deliver si RNA into cells for therapy, but also could realize SERS trace with high sensitivity and non-invasive features. The constructed delivery system has considerable potential to trace the dynamic gene delivery in living cells.     

Investigation on two triphenylene based electron transport materials

Promoting electron mobility is the key to designing high performance electron transport materials(ETMs). Formation of intermolecular interaction can be helpful to enhance their electron mobilities as a result of more ordered molecular stacking.Here, to reveal the inherent influence of intermolecular π-π stacking on the electron mobilities, we designed two ETMs, namely,2,4-diphenyl-6-[3-(2-triphenylenyl)phenyl]-1,3,5-triazine(TPTRZ) and 2,4-diphenyl-6-[4′-(2-triphenylenyl)[1,1′-biphenyl]-3-yl]-1,3,5-triazine(TPPTRZ). Thermal, photophysical and electrochemical measurement results indicate they are good ETM candidates. Additionally, TPTRZ and TPPTRZ exhibit high electron mobilities of 3.60×10~(-5) and 3.58×10~(-5) cm~2V-1 s~(-1), respectively, at an electric field of 7×10~5 V cm~(-1). By taking X-ray single crystal structure, theoretical calculation and time of flight(TOF) results into consideration, it is revealed that strong intermolecular π-π stacking induced by planar triphenylene and triphenyltriazine units renders TPTRZ and TPPTRZ small energetic and positional disorder parameters, and results in their high electron mobilities thereby. By further enhancing intermolecular π-π stacking, ETMs with even higher electron mobilities can thus be anticipated.     

An integrated micropump and electrospray emitter system based on porous silica monoliths

The work presents the design of an integrated system consisting of a high-pressure electroosmotic (EO) micropump and a microporous monolithic emitter, which together generate a stable and robust electrospray. Both the micropump and electrospray emitter are fabricated using a sol-gel process. Upon application of an electric potential of sufficient amplitude (>2 kV), the pump delivers fluids with an electroosmotically induced high pressure (>1 atm). The same potential is also harnessed to electrostatically generate a stable electrospray at the porous emitter. Electrokinetic coupling between pump and spray produces spray features different from sprays pressurized by independent mechanical pumps. Four typical spray modes, each with different drop sizes and charge-to-mass ratios, are observed and have been characterized. Since the monolith is silica-based, this integrated device can be used for a variety of fluids, especially organic solvents, without the swelling and shrinking problems that are commonly encountered for polymer monoliths. The maximum pressure generated by a 100 microm id monolithic pump is 3 atm at an applied voltage of 5 kV. The flow rate can be adjusted in the range of 100 nL/min to 1 microL/min by changing the voltage. For a given applied voltage across the pump and emitter system, it is seen that there exists one unique flow rate for which flow balance is achieved between the delivery of liquid to the emitter by the pump and the liquid ejection from the emitter. Under such a condition, a stable Taylor cone is obtained. The principles that lead to these results are also discussed.     

Advances in smart materials: Stimuli-responsive hydrogel thin films

This review highlights recent developments in the field of stimuli-responsive hydrogels, focusing primarily on thin films, with a thickness range between 100 nm to 10 μm. The theory and dynamics of hydrogel swelling is reviewed, followed by specific applications. Gels are classified based on the active stimulus—mechanical, chemical, pH, heat, and light—and fabrication methods, design constraints, and novel stimuli-responses are discussed. Often, these materials display large physiochemical reactions to a relatively small stimulus. Noteworthy materials larger than 10 μm, but with response times on the order of seconds to minutes are also discussed. Hydrogels have the potential to advance the fields of medicine and polymer science as useful substrates for “smart” devices. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1084–1099     

Inorganic p-type semiconductors and carbon materials based hole transport materials for perovskite solar cells

Incorporation of proper inorganic p-type semiconductors as hole transport layer has great potential to increase long-term stability while maintaining high power conversion efficiency of perovskite solar cells with low material cost.     

Magnetic properties of composite materials based on plant- or mineral-derived amorphous silica

Fe _x (O, OH) _y –SiO₂ composite samples are prepared. The composite matrix is amorphous silica prepared by controlled precipitation from silicate solutions or silica derived from rice husks. The iron is shown to exist in the form of acagenite β-FeO(OH) or hematite α-Fe₂O₃. The magnetic properties of the composites are studied at temperatures in the range 2–300 K and fields in the range ±5 T. The composite samples exhibit superparamagnetic properties.     

Structure and properties of porous film materials based on an aliphatic copolyamide

Phase segregation of solutions of ɛ-caprolactam-polyhexamethyleneadipamide copolymer in alcoholwater mixtures and the influence exerted on the pore structure and properties of film materials by the solution concentration and time of its keeping prior to deposition were studied.     

Diffusion characteristics of agarose hydrogel used in diffusive gradients in thin films for measurements of cations and anions

The agarose hydrogel has been increasingly used as a diffusive layer in diffusive gradients in thin films (DGT) measurements. However its diffusive characteristics have not been examined in detail. In this study, the performance of agarose gel was tested in DGT measurements of eight cations (Fe(II), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), and Cd(II)) and eight anions (P(V), As(V), Cr(VI), Mo(VI), Sb(V), Se(VI), V(V), and W(VI)). It was found that the thickness of agarose, a key parameter in the calculation of DGT measured concentration, remained unchanged after hydration followed by storage under the following conditions: pH 2–11, ionic strength 0–1.0 M, temperature 4–40 °C, and with the storage time extending to 300 d. Enrichment of cations and repelling of anions were observed in the gel under the ionic strengths of < 2–3 mM and <1 mM (NaNO₃), respectively, which was attributed to the electrostatic interactions of these ions with the fixed negatively charged groups (mainly pyruvate) in the gel. The diffusion coefficients of cations and anions through the agarose gel (plus a PVDF filter membrane) were on average 1.10 ± 0.04 times of the reported diffusion coefficients through the agarose cross-linked polyacrylamide (APA) hydrogel, typically used in DGT technique. The working pH ranges for the agarose gel-assembled DGTs were 4–10 and 5–9 for anions and cations, respectively. The use of agarose gel, either individually or along with different filter membranes, affected the overall diffusion rates of cations and anions. The measured DGT concentrations of cations and anions in filtered natural freshwater and seawater were mostly in line with those measured directly. The results showed that the agarose gel can be used as one of the standard diffusive layers in DGT measurements for a wide range of inorganic and organic analytes.     

Investigation of gas transport through porous membranes based on nonlinear frequency response analysis

Theoretical development of a new experimental method for investigation of mass transport in porous membranes, based on the principle of the modified Wicke-Kallenbach diffusion cell and the nonlinear frequency response analysis is presented. The method is developed to analyze the transport of a binary gas mixture in a porous membrane. The mixture is assumed to consist of one adsorbable and one inert component. Complex mass transfer mechanism in the membrane, where bulk or transition diffusion in the pore volume and surface diffusion take place in parallel, is assumed. Starting from the basic mathematical model equations and following a rather standardized procedure, the frequency response functions (FRFs) up to the second order are derived. Based on the derived FRFs, correlations between some characteristic features of these functions on one side, and the whole set of equilibrium and transport parameters of the system, on the other, are established. As the FRFs can be estimated directly from different harmonics of the measured outputs, these correlations give a complete theoretical basis for the proposed experimental method. The method is illustrated by quantifying the transport of helium (inert gas) and C₃H₈ and CO₂ (adsorbable gases) through a porous Vycor glass membrane.     

Ionic transport in porous media for high zeta potentials

Ionic transport coefficients are numerically calculated in various porous media for high zeta potentials zeta by solving the Poisson-Boltzmann, the Stokes, and the convection-diffusion equations on the pore scale. Theoretical formulae for the simple case of a plane Poiseuille flow are derived in this limit. These formulae, when expressed in terms of the characteristic length Lambda, provide an excellent estimate of the ionic transport coefficients whatever the porous medium and whatever the value of zeta.