Application of a clustered countercurrent-flow micro-channel reactor in the preparation of KMnF3 perovskite for asymmetric supercapacitors.

A clustered countercurrent-flow micro-channel reactor (C-CFMCR) with adjustable magnification times was constructed for the preparation of KMnF3 perovskite fluoride by a co-precipitation process, in which the concentrations and feed rates of reactants were precisely controlled. Benefitting from the enhanced micromixing efficiency of the microreactor, the KMnF3 particles prepared in C-CFMCR were smaller and less aggregated than those produced with traditional stirred reactors (STR). The prepared KMnF3 was applied as the electrode material in supercapacitors, and the electrochemical measurements showed that the KMnF3 obtained under optimal conditions had a discharge specific capacitance of ∼442 F g-1 at a current density of 1 A g-1, with a decline of ∼5.4% after 5000 charge-discharge cycles in an aqueous electrolyte of 2 M KOH. It was also found that the morphologies and electrochemical performances of the prepared KMnF3 particles changed accordingly with the micromixing efficiencies of C-CFMCR, which can be adjusted by the reactor structure and operating conditions. An asymmetric supercapacitor assembled with the KMnF3 and activated carbon exhibited an energy density of 13.1 W h kg-1 at a power density of 386.3 W kg-1, with eminent capacitance retention of ∼81.2% after 5000 cycles. In addition, only a slight amplification effect of C-CFMCR on the co-precipitation process was noticed, indicating that the C-CFMCR is a promising technology for the massive and controllable production of KMnF3 particles as well as other ultrafine particles.

Micromixing Study of a Clustered Countercurrent-Flow Micro-Channel Reactor and Its Application in the Precipitation of Ultrafine Manganese Dioxide.

A clustered countercurrent-flow micro-channel reactor (C-CFMCR) has been assembled by the numbering-up of its single counterpart (S-CFMCR). Its micromixing performance was then studied experimentally using a competitive parallel reaction system, and the micromixing time was calculated as the micromixing performance index. It was found that the micromixing time of C-CFMCR was ranged from 0.34 to 10 ms according to its numbering-up times and the operating conditions of the reactor, and it was close to that of S-CFMCR under the same operating conditions, demonstrating a weak scaling-up effect from S-CFMCR to C-CFMCR. The C-CFMCR was then applied to prepare ultrafine manganese dioxide in a continuous manner at varying micromixing time. It showed that the micromixing time had a major effect on the particle structure. More uniform and smaller MnO2 particles were obtained with intensified micromixing. By building a typical three electrode system to characterize their performance as a supercapacitor material, the MnO2 particles prepared by both S-CFMCR and C-CFMCR under optimal conditions displayed a specific capacitance of ~175 F·g-1 at the current density of 1 A·g-1, with a decline of ~10% after 500 charge-discharge cycles. This work showed that C-CFMCR will have a great potential for the continuous and large-scale preparation of ultrafine particles.

Improved biological effects of uniconazole using porous hollow silica nanoparticles as carriers.

BACKGROUND: The aim of this work is to prepare a controlled-release formulation of uniconazole using porous hollow silica nanoparticles (PHSNs) as carrier, and to investigate the biological effects on rice growth. RESULTS: PHSNs with a shell thickness of ~15 nm and a particle size of 80-100 nm were synthesised through a sol-gel route using nanosized calcium carbonate particles as templates. Simple immersing (SI) and supercritical fluid drug loading (SFDL) technologies were employed to load uniconazole into PHSNs with loading efficiencies of ~22 and ~26% respectively. The prepared uniconazole-loaded PHSNs (UCZ-PHSNs) by SI and SFDL both demonstrated sustained release properties, and the latter showed better controlled release ability with a slower release rate. Compared with free uniconazole, UCZ-PHSNs exhibited a weaker growth retardation effect in the early stage but more significant retardation ability in later stages for agar-cultured rice seedlings. For the rice that grew in clay, UCZ-PHSNs demonstrated a weaker plant height retardation effect than free uniconazole at the early jointing stage by foliar spraying, but exhibited a stronger retardation capacity than free uniconazole by being applied into soil before seedling transplantation. CONCLUSION: The results indicated that the prepared UCZ-PHSNs possessed good controlled-release properties and had improved retardation effects on rice growth. It is recommended that UCZ-PHSNs be applied into soil before seedling transplantation rather than administered by foliar spraying at the early jointing stage.

Selective hydrogenation of acetylene over egg-shell palladium nano-catalyst.

A novel egg-shell Pd/PHSNs nano-catalyst was prepared by a wet impregnation method using self-synthesized porous hollow silica nanoparticles (PHSNs) as support and applied in selective hydrogenation of acetylene to remove acetylene from the ethylene feed. By controlling the preparing conditions and calcining temperature, the active metal particles were loaded evenly on the support with a size about 5 nm. Compared with conventional catalysts prepared with solid silica nanoparticles, solid Al2O3 millispheres and a commercial catalyst, the Pd/PHSNs catalyst showed higher acetylene conversion rates at same reaction temperatures, and the porous hollow nano structure of PHSNs allowed smoother diffusion of ethylene molecules within the catalyst matrix so that ethylene could migrate away from the active sites in time to avoid turning into ethane, which resulted in superior ethylene selectivity at high acetylene conversion rates.

Development of egg-shell nano catalysts with porous hollow silica supports for hydrogenation.

Self-synthesized novel porous hollow silica nanoparticles (PHSNs) were applied as supports to prepare egg-shell nano catalysts for hydrogenation. By an impregnation method, different catalytic actives, such as Pd, Ag or Pt, and some promoters could be evenly loaded on the external surface, the pore channels and the internal surface of PHSNs. The prepared egg-shell catalysts were tested for CO hydrogenation and showed both improved activity and selectivity over those catalysts prepared with conventional support materials.

Adsorption of avermectin on porous hollow silica nanoparticles by supercritical technology.

Porous hollow silica nanoparticles with O.D. of approximately 100 nm and a wall thickness of approximately 10 nm were prepared by using inorganic CaCO3 templates. The produced PHSN were employed as a novel carrier to study the adsorption of avermectin in supercritical carbon dioxide by applying different adsorption pressure, adsorption temperature, adsorption time and volume of cosolvent. The results indicated that while increasing adsorption pressure and time always showed a positive effect on the avermectin adsorption until adsorption saturation is reached, both the adsorption temperature and volume of cosolvent require an optimal value for achieving the maximum adsorption. It was found that the optimal adsorption could be obtained at an adsorption pressure of 15 MPa and an adsorption temperature of 313 K for 90 minutes with 5 ml cosolvent. In addition, the desorption behavior of avermectin from the avermectin-loaded PHSN samples showed a sustained style: approximately 60% of avermectin was released in the first 20 minutes, while the other 40% followed a typical sustained desorption pattern and was dissolved out slowly for a time period of 3000 minutes, which is different from the quick and complete desorption from solid SiO2 carriers.

Study of UV-shielding properties of novel porous hollow silica nanoparticle carriers for avermectin.

The shielding protection given by self-prepared porous hollow silica nanoparticles (PHSN) to pesticides from degradation by UV light was investigated using avermectin as a model pesticide. It was demonstrated that PHSN carriers with a shell thickness of approximately 15 nm and a pore diameter of 4-5 nm have an encapsulation capacity of 625 g kg(-1) for avermectin using a supercritical fluid loading method. PHSN carriers exhibited remarkable UV-shielding properties for avermectin. This was affected by the intensity of UV light, the pH and the temperature of the release medium. Rises in UV intensity, pH and/or temperature reduced the UV protection of PHSN for avermectin. In addition, avermectin loaded into the inner core of the PHSN carriers was released slowly into the release medium for about 30 days following a typical sustained-release pattern. It thus appears that PHSN carriers have a promising future in applications requiring sustained pesticide release.

Transport of ions through the oil phase of W(1)/O/W(2) double emulsions.

Using a capillary video microscopy technique, the ion transport at liquid-liquid interfaces and through a surfactant-containing emulsion liquid membrane was visually studied by preparing a double emulsion globule within the confined space of a thin-walled, transparent, cylindrical microtube. NaCl and AgNO(3) were selected as the model reactants and were prepared to form a NaCl/AgNO(3) pair across the oil film. By observing and measuring the formed AgCl deposition, it was found that both Cl(-) and Ag(+) could transport through a thick oil film and Ag(+) was transported faster than Cl(-). Interestingly, the ion transport was significantly retarded when the oil film became extremely thin (<1 microm). The results suggested that the transport of ions mainly depends on the "reverse micelle transport" mechanism, in which reverse micelles with entrapped ions and water molecules can be formed in a thick oil film and their construction will get impeded if the oil film becomes extremely thin, leading to different ion transport rates in these two cases. The direction of ion transport depends on the direction of the osmotic pressure gradient across the oil film and the ion transport is independent of the oil film thickness in the investigated thick range. Ions with smaller Pauling radii are more easily entrapped into the formed reverse micelles and therefore will be transported faster through the oil film than bigger ions. Oil-soluble surfactants facilitate ion transport; however, too much surfactant in the oil film will slow down the ion migration. In addition, this study showed no support for the "molecular diffusion" mechanism of ion transport through oils.

Porous hollow silica nanoparticles as carriers for controlled delivery of ibuprofen to small intestine.

With two different methods, ibuprofen was entrapped into porous hollow silica nanoparticles (PHSNs) carriers, which were synthesized through a sol-gel route by using CaCO3 nanoparticles as the inorganic templates. By employing pressured CO2 as the loading medium, the amount of ibuprofen that was pressed into the carriers was approximately 52% higher than that by simply soaking. The drug release behaviors of the ibuprofen-loaded PHSNs were investigated in a simulated intestine juice and an artificial gastric fluid, respectively, and it demonstrated a sustained release pattern in all cases and the sample prepared under high pressure had a lower release rate in both fluids and thus owned a greater sustained drug release capacity. In the acidic artificial gastric fluid, no silica was degraded and only 16% of the loaded ibuprofen was released from the matrix in 300 min. However, much more silica was degraded in the simulated intestine juice in a shorter time and almost all the loaded ibuprofen was dissolved into the solution eventually, resulting in a quicker and complete ibuprofen release. Therefore, the PHSNs can be utilized for applications of controlled drug delivery to small intestine.

Controlled release of avermectin from porous hollow silica nanoparticles: influence of shell thickness on loading efficiency, UV-shielding property and release.

Preparation and characterization of porous hollow silica nanoparticles (PHSNs), with various shell thicknesses in the range of 5-45 nm and a pore diameter of about 4-5 nm, were investigated. PHSNs were fabricated via a sol-gel route with two different structure-directing templates and their shell thickness could be controlled by adjusting the reactant ratio of Na2SiO3.9H2O/CaCO3. The produced PHSNs were applied as controlled pesticide release carriers to study the effects of the shell thickness on the loading efficiency for avermectin, the UV-shielding property for the loaded avermectin and the controlled release of the loaded avermectin from the carriers. It was found that the amount of loaded avermectin decreases with the increase of shell thickness, while the UV-shielding property of PHSNs for avermectin is improved as the shell gets thicker. In addition, the shell thickness has a significant impact on avermectin release. Increasing the shell thickness in the range of 5-45 nm leads to a more sustained release by decreasing the release rate of the pesticide from PHSNs, showing that the shell thickness is one of the main controlling factors for the active agent release from such systems.

Controlled release of avermectin from porous hollow silica nanoparticles.

Porous hollow silica nanoparticles (PHSNs) with a diameter of ca 100 nm and a pore size of ca 4.5 nm were synthesized via a sol-gel route using inorganic calcium carbonate nanoparticles as templates. The synthesized PHSNs were subsequently employed as pesticide carriers to study the controlled release behaviour of avermectin. The avermectin-loaded PHSN (Av-PHSN) samples were characterized by BET, thermogravimetric analysis and IR, showing that the amount of avermectin encapsulated in the PHSN carrier could reach 58.3% w/w by a simple immersion loading method, and that most of the adsorption of avermectin on the Av-PHSN carrier might be physical. Avermectin may be loaded on the external surface, the pore channels in the wall and the inner core of the PHSN carriers, thus leading to a multi-stage sustained-release pattern from the Av-PHSN samples. Increasing pH or temperature intensified the avermectin release.

Fabrication of porous hollow silica nanoparticles and their applications in drug release control.

Preparation and characterization of porous hollow silica nanoparticles (PHSN) for controlled release applications were investigated. Through orthogonally designed experiments, the optimal synthesis conditions for the preparation of PHSN were obtained and the produced PHSN were characterized by BET, SEM, TEM and IR. Scanning and transmission electron microscopy images revealed their hollow shell-core structure and also demonstrated that the size and shape of PHSN are determined by the templating CaCO3 nanoparticles. The produced PHSN were applied as a carrier to study the controlled release behaviors of Brilliant Blue F (BB), which was used as a model drug. Being loaded into the inner core and on the surfaces of the nanoparticles, BB was released slowly into a bulk solution for about 1140 min as compared to only 10 min for the normal SiO2 nanoparticles, thus exhibited a typical sustained release pattern without any burst effect. In addition, higher BET of the carriers, lower pH value and lower temperature prolonged BB release from PHSN, while stirring speed showed little influence on the release behavior. It showed that PHSN have a promising future in controlled drug delivery applications.