Surface Area Determination of Particle-Based Mesoporous Films Using Krypton Physisorption.

One of the key characteristics of mesoporous films, making them attractive in many applications, is the surface enhancement gained by the porosity. Today, this attribute is rarely presented for particle-based mesoporous films. This work shows that krypton physisorption can be used to determine the available surface area of particle-based silica films synthesized by the direct growth (DiG) method. The surface area per substrate area of the films was measured to be 50-170 m2/m2 and the surface area per film volume was 310-490 m2/cm3 when the film thickness was varied between 100 and 520 nm. For comparison, a 105 nm thick film synthesized using dip-coating was used, as this technique renders more smooth films. The corresponding values for the dip-coated film was 90 m2/m2 and 880 m2/cm3, showing a higher surface area per film volume for the continuous film. The method is hence suitable for the characterization of mesoporous films synthesized with various techniques and can be used for the optimization of catalysts, drug delivery systems, and sensors.

Selectivity Control of Oxygen Reduction Reaction over Mesoporous Transition Metal Oxide Catalysts for Electrified Purification Technologies.

Direct electrification of oxygen-associated reactions contributes to large-scale electrical storage and the launch of the green hydrogen economy. The design of the involved catalysts can mitigate the electrical energy losses and improve the control of the reaction products. We evaluate the effect of the interface composition of electrocatalysts on the efficiency and productivity of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), both mechanistically and at device levels. The ORR and OER were benchmarked on mesoporous nickel(II) oxide and nickel cobaltite (NiO and NiCo2O4, respectively) obtained by a facile template-free hydrothermal synthesis. Physicochemical characterization showed that both NiO and NiCo2O4 are mesoporous and have a cubic crystal structure with abundant surface hydroxyl species. NiCo2O4 showed higher electrocatalytic activity in OER and selectivity to water as the terminal product of ORR. On the contrary, ORR over NiO yielded hydroxyl radicals as products of a Fenton-like reaction of H2O2. The product selectivity in ORR was used to construct two electrolyzers for electrified purification of oxygen and generation of hydroxyl radicals.

Nanocellulose composite wound dressings for real-time pH wound monitoring.

The skin is the largest organ of the human body. Wounds disrupt the functions of the skin and can have catastrophic consequences for an individual resulting in significant morbidity and mortality. Wound infections are common and can substantially delay healing and can result in non-healing wounds and sepsis. Early diagnosis and treatment of infection reduce risk of complications and support wound healing. Methods for monitoring of wound pH can facilitate early detection of infection. Here we show a novel strategy for integrating pH sensing capabilities in state-of-the-art hydrogel-based wound dressings fabricated from bacterial nanocellulose (BC). A high surface area material was developed by self-assembly of mesoporous silica nanoparticles (MSNs) in BC. By encapsulating a pH-responsive dye in the MSNs, wound dressings for continuous pH sensing with spatiotemporal resolution were developed. The pH responsive BC-based nanocomposites demonstrated excellent wound dressing properties, with respect to conformability, mechanical properties, and water vapor transmission rate. In addition to facilitating rapid colorimetric assessment of wound pH, this strategy for generating functional BC-MSN nanocomposites can be further be adapted for encapsulation and release of bioactive compounds for treatment of hard-to-heal wounds, enabling development of novel wound care materials.

Electrochemical investigation of carbon paper/ZnO nanocomposite electrodes for capacitive anion capturing.

In this work, we demonstrate an effective anion capturing in an aqueous medium using a highly porous carbon paper decorated with ZnO nanorods. A sol-gel technique was first employed to form a thin and compact seed layer of ZnO nanoparticles on the dense network of carbon fibers in the carbon paper. Subsequently, ZnO nanorods were successfully grown on the pre-seeded carbon papers using inexpensive chemical bath deposition. The prepared porous electrodes were electrochemically investigated for improved charge storage and stability under long-term operational conditions. The results show effective capacitive deionization with a maximum areal capacitance of 2 mF/cm2, an energy consumption of 50 kJ per mole of chlorine ions, and an excellent long-term stability of the fabricated C-ZnO electrodes. The experimental results are supported by COMSOL simulations. Besides the demonstrated capacitive desalination application, our results can directly be used to realize suitable electrodes for energy storage in supercapacitors.

Polyaniline inside the pores of high surface area mesoporous silicon as composite electrode material for supercapacitors.

Mesoporous silicon (mSi) obtained by the magnesiothermic reduction of mesoporous silica was used to deposit polyaniline (PANI) in its pores, the composite was tested for its charge storage application for high performance supercapacitor electrodes. The mesoporous silica as confirmed by Small Angle X-ray Scattering (SAXS) has a Brunauer-Emmett-Teller (BET) surface area of 724 m2g-1 and mean pore size of 5 nm. After magnesiothermic reduction to mSi, the BET surface area is reduced to 348 m2g-1 but the mesoporousity is retained with a mean pore size of 10 nm. The BET surface area of mesoporous silicon is among the highest for porous silicon prepared/reduced from silica. In situ polymerization of PANI inside the pores of mSi was achieved by controlling the polymerization conditions. As a supercapacitor electrode, the mSi-PANI composite exhibits better charge storage performance as compared to pure PANI and mesoporous silica-PANI composite electrodes. Enhanced electrochemical performance of the mSi-PANI composite is attributed to the high surface mesoporous morphology of mSi with a network structure containing abundant mesopores enwrapped by an electrochemically permeable polyaniline matrix.

Growth and Functionalization of Particle-Based Mesoporous Silica Films and Their Usage in Catalysis.

We report the formation of mesoporous films consisting of SBA-15 particles grown directly onto substrates and their usage as catalysts in esterification of acetic acid and ethanol. The film thickness was altered between 80 nm and 750 nm by adding NH4F to the synthesis solution. The salt also affects the formation rate of the particles, and substrates must be added during the formation of the siliceous network in the solution. Various substrate functionalizations were tested and hydrophobic substrates are required for a successful film growth. We show that large surfaces (> 75 cm²), as well as 3D substrates, can be homogenously coated. Further, the films were functionalized, either with acetic acid through co-condensation, or by coating the films with a thin carbon layer through exposure to furfuryl alcohol fumes followed by carbonization and sulfonation with H2SO4. The carbon-coated film was shown to be an efficient catalyst in the esterification reaction with acetic acid and ethanol. Due to the short, accessible mesopores, chemical variability, and possibility to homogenously cover large, rough surfaces. the films have a large potential for usage in various applications such as catalysis, sensing, and drug delivery.

Impact of the morphological and chemical properties of copper-zirconium-SBA-15 catalysts on the conversion and selectivity in carbon dioxide hydrogenation.

A hybrid catalyst consisting of Zr-doped mesoporous silica (Zr-SBA-15) supports with intergrown Cu nanoparticles was used to study the effects of a catalyst's chemical states on CO2 hydrogenation. The chemical state of the catalyst was altered by using tetraethyl orthosilicate (TEOS) or sodium metasilicate (SMS) as the silica precursor in the synthesis of the Zr-SBA-15 framework, and infiltration (Inf) or evaporation induced wetness impregnation (EIWI) as the Cu loading method. As a result, the silica precursor mainly affects the activity of the catalyst whereas the Cu loading method alters the selectivity of the products. TEOS materials exhibit a higher catalytic activity compared to SMS materials due to different Zr dispersion and bonding to the silica matrix. EIWI catalysts display selectivity for methanol formation, while the Inf ones enable methanol conversion to DME. This is correlated to a higher Zr content and lower Cu oxidation states of EIWI prepared catalysts.

Cell adherence and drug delivery from particle based mesoporous silica films.

Spatially and temporally controlled drug delivery is important for implant and tissue engineering applications, as the efficacy and bioavailability of the drug can be enhanced, and can also allow for drugging stem cells at different stages of development. Long-term drug delivery over weeks to months is however difficult to achieve, and coating of 3D surfaces or creating patterned surfaces is a challenge using coating techniques like spin- and dip-coating. In this study, mesoporous films consisting of SBA-15 particles grown onto silicon wafers using wet processing were evaluated as a scaffold for drug delivery. Films with various particle sizes (100-900 nm) and hence thicknesses were grown onto trichloro(octadecyl)silane-functionalized silicon wafers using a direct growth method. Precise patterning of the areas for film growth could be obtained by local removal of the OTS functionalization through laser ablation. The films were incubated with the drug model 3,3'-dioctadecyloxacarbocyanine perchlorate (DiO), and murine myoblast cells (C2C12 cells) were seeded onto films with different particle sizes. Confocal laser scanning microscopy (CLSM) was used to study the cell growth, and a vinculin-mediated adherence of C2C12 cells on all films was verified. The successful loading of DiO into the films was confirmed by UV-vis and CLSM. It was observed that the drugs did not desorb from the particles during 24 hours in cell culture. During adherent growth on the films for 4 h, small amounts of DiO and separate particles were observed inside single cells. After 24 h, a larger number of particles and a strong DiO signal were recorded in the cells, indicating a particle mediated drug uptake. The vast majority of the DiO-loaded particles remained attached to the substrate also after 24 h of incubation, making the films attractive as longer-term reservoirs for drugs on e.g. medical implants.

Nanoporous Ca3Co4O9 Thin Films for Transferable Thermoelectrics.

The development of high-performance and transferable thin-film thermoelectric materials is important for low-power applications, e.g., to power wearable electronics, and for on-chip cooling. Nanoporous films offer an opportunity to improve thermoelectric performance by selectively scattering phonons without affecting electronic transport. Here, we report the growth of nanoporous Ca3Co4O9 thin films by a sequential sputtering-annealing method. Ca3Co4O9 is promising for its high Seebeck coefficient and good electrical conductivity and important for its nontoxicity, low cost, and abundance of its constituent raw materials. To grow nanoporous films, multilayered CaO/CoO films were deposited on sapphire and mica substrates by rf-magnetron reactive sputtering from elemental Ca and Co targets, followed by annealing at 700 °C to form the final phase of Ca3Co4O9. This phase transformation is accompanied by a volume contraction causing formation of nanopores in the film. The thermoelectric propoperties of the nanoporous Ca3Co4O9 films can be altered by controlling the porosity. The lowest electrical resistivity is ∼7 mΩ cm, yielding a power factor of 2.32 × 10-4 Wm-1K-2 near room temperature. Furthermore, the films are transferable from the primary mica substrates to other arbitrary polymer platforms by simple dry transfer, which opens an opportunity of low-temperature use these materials.

Formation of block-copolymer-templated mesoporous silica.

In situ attenuated total reflectance Fourier transform infrared spectroscopy is used to monitor the chemical evolution of the mesoporous silica SBA-15 from hydrolysis of the silica precursor to final silica condensation after the particle formation. Two silica precursors, tetraethyl orthosilicate (TEOS) or sodium metasilicate (SMS) were used, and the effects of additive (heptane and NH4F) concentrations were studied. Five formation stages are identified when TEOS is used as the precursor. The fourth stage correlates with the appearance and evolution of diffraction peaks recorded using in situ small angle X-ray diffraction. Details of the formed silica matrix are observed, e.g. the ratio between six-fold cyclic silica rings and linear bonding increases with the NH4F concentration. The TEOS hydrolysis time is independent of the NH4F concentration for small amounts of heptane, but is affected by the size of the emulsion droplets when the heptane amount increases. Polymerization and condensation rates of both silica precursors are affected by the salt concentration. Materials synthesized using SMS form significantly faster compared to TEOS-materials due to the pre-hydrolysis of the precursor. The study provides detailed insights into how the composition of the synthesis solution affects the chemical evolution and micellar aggregation during formation of mesoporous silica.

Mesoporous Silica-gold Films for Straightforward, Highly Reproducible Monitoring of Mercury Traces in Water.

Trace-level detection of mercury in waters is connected with several complications including complex multistep analysis routines, applying additional, harmful reagents increasing the risk of contamination, and the need for expensive analysis equipment. Here, we present a straightforward reagent-free approach for mercury trace determination using a novel thin film sampling stick for passive sampling based on gold nanoparticles. The nanoparticles supported on a silicon wafer and further covered with a thin layer of mesoporous silica. The mesoporous silica layer is acting as a protection layer preventing gold desorption upon exposure to water. The gold nanoparticles are created by thermal treatment of a homogenous gold layer on silicon wafer prepared by vacuum evaporation. This gold-covered substrate is subsequently covered by a layer of mesoporous silica through dip-coating. Dissolved mercury ions are extracted from a water sample, e.g., river water, by incorporation into the gold matrix in a diffusion-controlled manner. Thus, the amount of mercury accumulated during sampling depends on the mercury concentration of the water sample, the accumulation time, as well as the size of the substrate. Therefore, the experimental conditions can be chosen to fit any given mercury concentration level without loss of sensitivity. Determination of the mercury amount collected on the stick is performed after thermal desorption of mercury in the gas phase using atomic fluorescence spectrometry. Furthermore, the substrates can be re-used several tens of times without any loss of performance, and the batch-to-batch variations are minimal. Therefore, the nanogold-mesoporous silica sampling substrates allow for highly sensitive, simple, and reagent-free determination of mercury trace concentrations in waters, which should also be applicable for on-site analysis. Successful validation of the method was shown by measurement of mercury concentration in the certified reference material ORMS-5, a river water.

Targeted delivery of a novel anticancer compound anisomelic acid using chitosan-coated porous silica nanorods for enhancing the apoptotic effect.

Targeted cancer therapies are currently a strong focus in biomedical research. The most common approach is to use nanocarrier-based targeting to specifically deliver conventional anticancer drugs to enhance their therapeutic efficacy, increase bioavailability, and decrease the side-effects on normal cells. A step further towards higher specificity and efficacy would be to employ specific novel drugs along with specific nanocarrier-based targeting. Our recent studies have demonstrated that a plant-derived diterpenoid compound, anisomelic acid (AA), induces apoptosis in cervical cancer cells. In this work, we describe the development of a folic acid (FA)-targeted AA delivery system using chitosan-coated rod-shaped mesoporous silica particles (Chitosan-NR-MSP). The cellular internalization and uptake enhancement of the FA-Chitosan-NR-MSP towards cancerous folate receptor (FR)-positive (SiHa and HeLa) and/or normal FR-negative (HEK 293) cells were assessed, which indicated that the intracellular uptake of FA-conjugated Chitosan-NR-MSP was more target-specific. Furthermore, the induction of apoptosis by AA-loaded chitosan-coated rod-shaped particles on SiHa cells was studied. By employing caspase-3 activation and PARP cleavage as measure of apoptosis, the FA-particle mediated AA treatment was clearly more effective, significantly enhancing apoptosis in comparison to non-targeted Chitosan-NR-MSP or free AA in SiHa cells, suggesting that the FA-Chitosan-NR-MSPs can be potentially utilized as a drug delivery system for cervical cancer treatment.

Single-pot synthesis of ordered mesoporous silica films with unique controllable morphology.

Mesoporous silica films consisting of a monolayer of separated SBA-15 particles with unusually wide and short pores grown on silicon wafers have been fabricated in a simple single-pot-synthesis, and the formation of the films has been studied. A recipe for synthesizing mesoporous silica rods with the addition of heptane and NH4F at low temperature was used and substrates were added to the synthesis solution during the reaction. The films are ~90 nm thick, have a pore size of 10.7-13.9 nm depending on the hydrothermal treatment time and temperature, and a pore length of 200-400 nm. All pores are parallel to the substrate, open, and easy to access, making them suitable for applications such as catalyst hosts and gas separation. The growth of the films is closely correlated to the evolution of the mesoporous silica particles. Here, we have studied the time for adding substrates to the synthesis solution, the evolution of the films with time during formation, and the effect of hydrothermal treatment. It was found that the substrates should be added within 30-60s after turning off the stirring and the films are formed within 10 min after addition to the synthesis solution. The study has yielded a new route for synthesizing mesoporous silica films with a unique morphology.

Tuning the shape of mesoporous silica particles by alterations in parameter space: from rods to platelets.

The knowledge of how to control the pore size and morphology of separated mesoporous silica particles is crucial for optimizing their performance in applications, such as molecular sieves and drug delivery systems. In this work, we have systematically studied the effects of various synthesis parameters to gain a deeper understanding of how particle morphologies can be altered. It was found that the morphology for isolated particles of SBA-15 type, with unusually short and wide pores, could be altered from rods to platelets by variations in the NH4F concentration. The pore length is nearly constant (~300 nm) for the different morphologies, but the particle width is increasing from 200 nm to >3 µm when decreasing the amount of NH4F, and the pore size can be tuned between 10 and 13 nm. Furthermore, other synthesis parameters such as heptane concentration, pH, silica precursor, and additions of ions have also been studied. The trend regarding particle width is independent of heptane concentration, at the same time as heptane increases the particle length up to a plateau value of ~500 nm. In all, parameters controlling particle width, length, and pore size have been separated in order to evaluate their function in the particle formation. Additionally, it was found that the formation time of the particles is strongly affected by the fluoride ion concentration, and a mechanism for particle formation for this system, where micelles transform from a foam, to multilamellar vesicles, and finally to cylindrical micelles, is suggested.