Ocean Cheung

K+ Exchanged Zeolite ZK-4 as a Highly Selective Sorbent for CO2

Adsorbents with high capacity and selectivity for adsorption of CO2 are currently being investigated for applications in adsorption-driven separation of CO2 from flue gas. An adsorbent with a particularly high CO2-over-N2 selectivity and high capacity was tested here. Zeolite ZK-4 (Si:Al ∼ 1.3:1), which had the same structure as zeolite A (LTA), showed a high CO2 capacity of 4.85 mmol/g (273 K, 101 kPa) in its Na(+) form. When approximately 26 at. % of the extraframework cations were exchanged for K(+) (NaK-ZK-4), the material still adsorbed a large amount of CO2 (4.35 mmol/g, 273 K, 101 kPa), but the N2 uptake became negligible (<0.03 mmol/g, 273 K, 101 kPa). The majority of the CO2 was physisorbed on zeolite ZK-4 as quantified by consecutive volumetric adsorption measurements. The rate of physisorption of CO2 was fast, even for the highly selective sample. The molecular details of the sorption of CO2 were revealed as well. Computer modeling (Monte Carlo, molecular dynamics simulations, and quantum chemical calculations) allowed us to partly predict the behavior of fully K(+) exchanged zeolite K-ZK-4 upon adsorption of CO2 and N2 for Si:Al ratios up to 4:1. Zeolite K-ZK-4 with Si:Al ratios below 2.5:1 restricted the diffusion of CO2 and N2 across the cages. These simulations could not probe the delicate details of the molecular sieving of CO2 over N2. Still, this study indicates that zeolites NaK-ZK-4 and K-ZK-4 could be appealing adsorbents with high CO2 uptake (∼4 mmol/g, 101 kPa, 273 K) and a kinetically enhanced CO2-over-N2 selectivity.

Aluminophosphate monoliths with high CO 2 -over- N 2 selectivity and CO 2 capture capacity

Monoliths of microporous aluminophosphates (AlPO4-17 and AlPO4-53) were structured by binder-free pulsed current processing. Such monoliths could be important for carbon capture from flue gas. The AlPO4-17 and AlPO4-53 monoliths exhibited a tensile strength of 1.0 MPa and a CO2 adsorption capacity of 2.5 mmol g � 1 and 1.6 mmol g � 1 , respectively at 101 kPa and 0 � C. Analyses of single component CO2 and N2 adsorption data indicated that the AlPO4-53 monoliths had an extraordinarily high CO2-over-N2 selectivity from a binary gas mixture of 15 mol% CO2 and 85 mol% N2. The estimated CO2 capture capacity of AlPO4-17 and AlPO4-53 monoliths in a typical pressure swing adsorption (PSA) process at 20 � C was higher than that of the commonly used zeolite 13X granules. Under cyclic sorption conditions, AlPO4-17 and AlPO4-53 monoliths were regenerated by lowering the pressure of CO2. Regeneration was done without application of heat, which would regenerate them to their full capacity for CO2 adsorption.

Nanostructure and pore size control of template-free synthesised mesoporous magnesium carbonate

The structure of mesoporous magnesium carbonate (MMC) first presented in 2013 is investigated using a bottom-up approach. MMC is found to be built from the aggregation of nanoparticles of amorphous MgCO3 and MgO with a coating of amorphous MgCO3. The nanoparticles have dimensions of approximately 2–5 nm as observed using transmission electron microscopy and the aggregation of the particles creates the pore structure of MMC. We further show that the average pore diameter of MMC can be controlled by varying the temperature during the powder formation process and demonstrate that altering the pore size opens the possibility to tune the amorphous phase stabilisation properties that MMC exerts on poorly soluble drug compounds. Specifically, we show the loading and release of the antifungal drug itraconazole using MMC as a drug carrier.

Effects of amine modification of mesoporous magnesium carbonate on controlled drug release

(3-Aminopropyl)triethoxysilane (APTES) was used to modify the surface of mesoporous magnesium carbonate (MMC). The as-synthesized MMC had an average pore diameter of ∼5nm, but amine grafting occurred preferentially on the walls of the largest MMC pores. Analysis of ibuprofen (IBU) loading and release showed that IBU remained stable in the amorphous phase in all the MMC and modified MMC samples. The kinetics of IBU release from the modified MMC were assessed and used to evaluate the effects of the different functional groups. The release rate showed that the release of IBU could be controlled by adjusting the amine surface coverage of MMC and also by changing the surface groups. It was concluded that the interaction between the grafted functional groups in the modified MMC and the OH in the carboxyl groups of IBU was the most important factor for prolonging the release of the drug. These results are expected to lead to investigation of other as yet unexplored applications for MMC, including using it as a plastic additive and for gas separation.

Study of mesoporous magnesium carbonate in contact with whole human blood

The interaction of mesoporours magnesium carbonate (Upsalite) particles (50–100 μm) with human whole blood was investigated using an in vitro loop model and the effect on the complement system, blood coagulation and red blood cell lysis was assessed. The removal of Ca2+ by Upsalite and the possible exchange with and/or release of Mg2+ were explored as well. Upsalite was found to present anticoagulant properties, most probably due to the uptake of Ca2+ by the particles. No hemolytic activity was detected at Upsalite concentrations up to 1 mg ml−1. Moderate to high levels of C3a and sC5b-9 were observed for Upsalite, however such levels were statistically different from the negative control only when the particle concentrations were 0.25 mg ml−1 and 1.0 mg ml−1, respectively. The presented findings are promising for the future development of mesoporous magnesium carbonate-based materials for biomedical applications.

A Modified In Situ Method to Determine Release from a Complex Drug Carrier in Particle-Rich Suspensions.

Effective and compound-sparing methods to evaluate promising drug delivery systems are a prerequisite for successful selection of formulations in early development stages. The aim of the study was to develop a small-scale in situ method to determine drug release and supersaturation in highly concentrated suspensions of enabling formulations. Mesoporous magnesium carbonate (MMC), which delivers the drug in an amorphous form, was selected as a drug carrier. Five model compounds were loaded into the MMC at a 1:10 ratio using a solvent evaporation technique. The μDiss Profiler was used to study the drug release from MMC in fasted-state simulated intestinal fluid. To avoid extensive light scattering previously seen in particle-rich suspensions in the μDiss Profiler, an in-house-designed protective nylon filter was placed on the in situ UV probes. Three types of release experiments were conducted for each compound: micronized crystalline drug with MMC present, drug-loaded MMC, and drug-loaded MMC with 0.01% w/w hydroxypropyl methyl cellulose. The nylon filters effectively diminished interference with the UV absorption; however, the release profiles obtained were heavily compound dependent. For one of the compounds, changes in the UV spectra were detected during the release from the MMC, and these were consistent with degradation of the compound. To conclude, the addition of protective nylon filters to the probes of the μDiss Profiler is a useful contribution to the method, making evaluations of particle-rich suspensions feasible. The method is a valuable addition to the current ones, allowing for fast and effective evaluation of advanced drug delivery systems.

Amorphous Calcium Carbonate Constructed from Nanoparticle Aggregates with Unprecedented Surface Area and Mesoporosity

Amorphous calcium carbonate (ACC), with the highest reported specific surface area of all current forms of calcium carbonate (over 350 m2 g-1), was synthesized using a surfactant-free, one-pot method. Electron microscopy, helium pycnometry, and nitrogen sorption analysis revealed that this highly mesoporous ACC, with a pore volume of ∼0.86 cm3 g-1 and a pore-size distribution centered at 8-9 nm, is constructed from aggregated ACC nanoparticles with an estimated average diameter of 7.3 nm. The porous ACC remained amorphous and retained its high porosity for over 3 weeks under semi-air-tight storage conditions. Powder X-ray diffraction, large-angle X-ray scattering, infrared spectroscopy, and electron diffraction exposed that the porous ACC did not resemble any of the known CaCO3 structures. The atomic order of porous ACC diminished at interatomic distances over 8 Å. Porous ACC was evaluated as a potential drug carrier of poorly soluble substances in vitro. Itraconazole and celecoxib remained stable in their amorphous forms within the pores of the material. Drug release rates were significantly enhanced for both drugs (up to 65 times the dissolution rates for the crystalline forms), and supersaturation release of celecoxib was also demonstrated. Citric acid was used to enhance the stability of the ACC nanoparticles within the aggregates, which increased the surface area of the material to over 600 m2 g-1. This porous ACC has potential for use in various applications where surface area is important, including adsorption, catalysis, medication, and bone regeneration.

Bismuth coordination polymers : from centuries-old medicines to unprecedented topological complexity

Bismuth coordination polymers : from centuries-old medicines to unprecedented topological complexity

Highly selective uptake of carbon dioxide on the zeolite vertical bar Na10.2KCs0.8 vertical bar-LTA - a possible sorbent for biogas upgrading

The|Na10.2KCs0.8|8[Al12Si12O48]8(Fm3[combining macron]c)-LTA zeolite adsorbs CO2-over-CH4 with a high selectivity (over 1500). The uptake of carbon dioxide is also high (3.31 mmol g(-1), 293 K, 101 kPa). This form of zeolite A is a very promising adsorbent for applications such as biogas upgrading, where keeping the adsorption of methane to a minimum is crucial.