Experimental Volumetric Hydrogen Uptake Determination at 77 K of Commercially Available Metal-Organic Framework Materials

Storage is still limiting the implementation of hydrogen as an energy carrier to integrate the intermittent operation of renewable energy sources. Among different solutions to the currently used compressed or liquified hydrogen systems, physical adsorption at cryogenic temperature in porous materials is an attractive alternative due to its fast and reversible operation and the resulting reduction in storage pressure. The feasibility of cryoadsorption for hydrogen storage depends mainly on the performance of the used materials for the specific application, where metal-organic frameworks or MOFs are remarkable candidates. In this work, gravimetric and volumetric hydrogen uptakes at 77 K and up to 100 bar of commercially available MOFs were measured since these materials are made from relatively cheap and accessible building blocks. These materials also show relatively high porous properties and are currently near to large-scale production. The measuring device was calibrated at different room temperatures to calculate an average correction factor and standard deviation so that the correction deviation is included in the measurement error for better comparability with different measurements. The influence of measurement conditions was also studied, concluding that the available adsorbing area of material and the occupied volume of the sample are the most critical factors for a reproducible measurement, apart from the samples’ preparation before measurement. Finally, the actual volumetric storage density of the used powders was calculated by directly measuring their volume in the analysis cell, comparing that value with the maximum volumetric uptake considering the measured density of crystals. From this selection of commercial MOFs, the materials HKUST-1, PCN-250(Fe), MOF-177, and MOF-5 show true potential to fulfill a volumetric requirement of 40 g·L−1 on a material basis for hydrogen storage systems without further packing of the powders.

O2 Physisorption in Coal Pore: Effects of Pore Size, Pressure, Temperature and Function Group

In this paper, the physical adsorption characteristics of oxygen in coal pores were systematically investigated by the Grand Canonical Monte Carlo and the COMPASS force field. Firstly, coal pore structures of different sizes were constructed by graphite slit models and different groups. Secondly, the physisorption behavior of oxygen in graphite slit models of different sizes was simulated. Finally, the physisorption behavior of oxygen in graphite slit models at different pressures and temperatures was analyzed. The results showed that the physisorption density and excess physical adsorption of oxygen were divided into the rapidly decreasing stage (0.4-0.7 nm), the slowly decreasing stage (0.7-1.4 nm), and the stable stage (1.4 nm-5 nm) with the increase of coal pores, and the excess oxygen physisorption amount was more sensitive to the change of pressure. The O2 isosteric heat of physisorption decreased with increasing pore size of coal. Oxygen is more strongly adsorbed by hydroxyl and ether bonds than by methyl, carboxyl and carbonyl groups. Through this study, the mechanism of oxygen physical adsorption in coal pores and the characteristics influenced by temperature and pressure can be better understood.

Methane adsorption onto silicas with various degree of hydrophobicity

The methane adsorption onto a hydrated surface of hydrophobic silica AM1 alone and impregnated by arginine, and silica gel Si-100 has been studied using low-temperature 1H NMR spectroscopy. It has been shown that the methane adsorption onto the AM1 surface depends on the degree of hydration and pretreatment type. The maximum adsorption (up to 80 mg/g) is observed for a sample hydrated after complete drying. It has been established that the adsorption is determined by a number of clusters of bound water of small radii. Based on a shape of the temperature dependence of the adsorption, it has been assumed that not only physical adsorption occurs, but also the quasi-solid methane hydrates are formed. It has been established that the amount of methane adsorbed onto a surface of a composite system AM1/arginine under isobaric conditions increases by tens of times (from 0.5 to 80 mg/g) in the presence of pre-adsorbed water pre-adsorbed at the surface. Probable mechanisms of the methane adsorption are physical adsorption on a surface, condensation in narrow voids between silica nanoparticles and nano-scaled (1-10 nm) water clusters, and the formation of solid (clathrate) methane hydrates. Water, adsorbed at a surface in a wide range of hydration, forms various clusters. This water is mainly strongly associated and characterized by chemical shifts in the range dH = 4-6 ppm. The hydrate structures with methane/water are quite stable and can exist even in the chloroform medium. However, in this case, a part of water transforms into a weakly associated state and it is observed at dH = 1.5-2 ppm.

Electrochemical and microscopic analysis on corrosion behavior of steel bars in slag/fly ash-cement paste subjected to seawater attack

series of corrosion experiments of cement paste-steel bar specimens with different contents of slag and fly ash were performed to investigate the influence of slag/fly ash on the corrosion behavior of steel bars in concrete under seawater. In this investigation, the corrosion behavior of specimen was electrochemically monitored by open-circuit potential (OCP), Tafel polarization (TP) and electrochemical impedance spectra (EIS). Meanwhile, SEM/EDS and XRD were applied to microscopically analyze the microstructure deterioration of materials. Results showed that, replacing cement with slag/fly ash caused a decrease in Ca(OH)2 as well as an increase in C-S-H gel and Friedel's salt in concrete, which can improve the chloride-solidification ability and slow down the chloride diffusion in concrete by both physical adsorption and chemical binding, and thereafter promoting the corrosion resistance of steel bars in concrete in marine environment. Compared to slag, the equal replacing content of fly ash can contribute to a better improving effect on the corrosion resistance of reinforced concrete in marine environment. In this study, a replacement of cement by 20% slag+20% fly ash led to an optimum improving effect on its corrosion resistance. In addition, the results also indicate that the corrosion of reinforced concrete caused by seawater attack does not occur at a uniform rate, but it can firstly maintain a long-term uncorroded state, and then develops rapidly after pitting corrosion occurs.

THE AMMONIA VAPORS INFLUENCE ON THE ELECTRICAL CHARACTERISTICS OF NANOSIZED TIN DIOXIDE FILMS OBTAINED USING A POLYMER

In the presented paper the effect of ammonia vapors on the electrical properties of nanosized tin dioxide films obtained using polymers was investigated to assess the possibility of their use as an ammonia sensor’s sensitive element at room temperature. Ammonia vapor leads to a decrease in the conductivity of the studied SnO2 films. This is due to the fact that the adsorbed ammonia molecules increase the height of the intergranular potential barriers, and the surface shut-off bend of the energy bands. The main role in this is played by the processes of physical adsorption of ammonia molecules. The sensitivity of the films to ammonia vapor is in the range of 0.35-0.63 and reaches a maximum at a voltage of 300 V. The processes of adsorption and desorption take place in two stages and are reversible, as evidenced by the calculated time constants of adsorption and desorption.

Size- and concentration-dependence of antiviral and virucidal activity of Au nanoparticles against adenoviruses and influenza viruses H1N1

Over the past 10 years, many scientific groups have experimentally shown that non-functionalized nanoparticles show a pronounced antiviral and antimicrobial action against different pathogens. In order to understand the mechanism of nanoparticles action it is important to know its peculiarities, i.e. dependences on different nanoparticles and pathogen properties.In this work we studied how Au nanoparticles act on the viruses outside and inside the cell, and compare this action for two sizes of nanoparticles and two types of the viruses. The study has been conducted for adenovirus and H1N1 influenza virus, and nanoparticles of 5 nm and 20 nm diameter.Virucidal and antiviral actions were observed experimentally for both types of nanoparticles against both viruses. It has been shown that intensity of virucidal action depends on the nanoparticles concentration non-monotonically for adenovirus. It has also been shown with electron microscopy that the viruses are destructed after 5 nm nanoparticles adsorption on their surface; and that the viruses change their shape after 20 nm nanoparticles adsorption on their surface. The model of physical adsorption of nanoparticles on the virus surface due to near-field interaction proposed in previous works may explain observed results on virucidal action of nanoparticles.

Anti-Corrosion Mechanism of Parsley Extract and Synergistic Iodide as Novel Corrosion Inhibitors for Carbon Steel-Q235 in Acidic Medium by Electrochemical, XPS and DFT Methods

The parsley extract (PLE) was prepared using absolute ethyl alcohol. The PLE and synergistic iodide were firstly utilized as efficacious corrosion inhibitors to slow down the corrosion rate of carbon steel-Q235 in 0.5 mol/L H2SO4 solution. The anti-corrosion performance was researched by weight loss method, electrochemical tests, surface analysis and quantum chemistry calculation. Results of electrochemical and weight loss tests show that the synergetic PLE and I− exhibit the optimal corrosion inhibition efficiency 99%. The combined inhibitor displays the favorable long-term corrosion inhibition effect, and the inhibition efficiency can maintain more than 90% after 144 h immersion. The introduction of I− makes carbon steel surface with higher negative charge amount, which could be beneficial to the interaction between corrosion inhibitor and Fe atoms. The adsorption behavior obeys the Langmuir isotherm adsorption, and involves chemical and physical adsorption. On the basis of electrochemical consequences and theoretical calculation, the adsorption process and anti-corrosion mechanisms are further explored.

Chemically Dual-Modified Biochar for the Effective Removal of Cr(VI) in Solution

Here, a dual-modification strategy using KMnO4 (potassium permanganate) and AlCl3·6H2O (aluminum chloride, hexahydrate) as co-modifiers to improve the Cr(VI) removal capacity of K2CO3 activated biochar is introduced. As a result, the dual-modified biochar with KMnO4 and AlCl3·6H2O has the calculated adsorption energy of −0.52 eV and −1.64 eV for HCrO4−, and −0.21 eV and −2.01 eV for Cr2O72−. The Al2O3 (aluminum oxide) and MnO (manganese oxide) embedded on the surface of dual-modified biochar bring more Cr(VI) absorption sites comparing to single-modified biochar, resulting in a maximum Cr(VI) saturated adsorption capacity of 152.86 mg g−1. The excellent removal performance is due to the synthetic effect of electrostatic attraction, reduction reaction, complexation reaction, and physical adsorption. The experimental results also indicated that the spontaneous adsorption process agreed well with the pseudo-second order and Langmuir models. This dual-modification strategy is not limited to the treatment of Cr(VI) with biochar, and may also be incorporated with the treatment of other heavy metals in aqueous environment.

New Cellulose based pH-Sensitive Hydrogel for Highly Efficient Dyes Removal in Water Treatment: Kinetic, Thermodynamic, Theoretical and Computational Studies

In this paper, a new green pH-sensitive cellulose based hydrogel (swelling rate ~ 1005 %) was successfully elaborated. However, the new EDTA crosslinked HEC was investigated as adsorbent materiel, which it showed high removal efficiency (~2000 mg.g-1) to aquatic micropollutants, especially methylene blue as cationic dyes model. The synthesis of HEC-EDTA at high advanced crosslinking degree (up to 92 %) that confirmed using structural analyzes (FTIR and 13C CP/MAS-NMR), was cried out using DAEDT and DMAP as acyl transfer agent, where the lamellar morphology (2D- microstructure) was highly suggested basing on the average functionality of the reaction system. The kinetic study showed that the adsorption process was better described by pseudo-second-order kinetic, where the thermodynamic parameters exhibited a negative effect of temperature indicating a physical adsorption process. In addition, the adsorption capacity was studied according to the experimental conditions (pH, contact time, concentration, etc.), and the Freundlich model revealed a strong correlation to the experimental results indicating an energetic heterogeneity of the surface active sites. In the other hand, molecular dynamics (MD) simulations were conducted and optimized using COMPASS II, where the results showed a good agreement with the experiment, and that basing on the intermolecular Non-covalent interaction, molecular structure and cluster configurations.

Partial purification, characterization and immobilization of a novel lipase from a native isolate of Lactobacillus fermentum

Background and Objectives: Due to the widespread use of lipase enzymes in various industries, finding native lipase pro- ducing microorganisms is of great value and importance. In this study, screening of lipase-producing lactobacilli from native dairy products was performed. Materials and Methods: Qualitative evaluation of lipolytic activity of lipase-producing lactobacilli was performed in differ- ent media containing olive oil. A clear zone observation around the colonies indicated the lipolytic activity. The strain with the highest enzymatic activity was identified. Determination of optimal pH and temperature of lipase activity was measured by spectrophotometry using p-nitrophenyl acetate (ρ-NPA) substrate. Partial purification of lipase enzyme was performed using 20-90% saturation ammonium sulfate. Eventually, lipase was immobilized by physical adsorption on chitosan beads. Results: Among screened lipolytic bacterial strains, one sample (5c isolate) which showed the highest enzymatic activity (5329.18 U/ml) was close to Lactobacillus fermentum. During characterization, the enzyme showed maximum activity in Tris-HCl buffer with pH 7, while remaining active over a temperature range of 5°C to 40°C. The results of the quantitative assay demonstrated that the fraction precipitated in ammonium sulfate at 20% saturation has the highest amount of lipolytic activity, with a specific activity of 22.0425 ± 3.6 U/mg. Purification folds and yields were calculated as 8.73 and 44%, respec- tively. Eventually, the enzyme was immobilized by physical adsorption on chitosan beads with a yield of 56.21%. Conclusion: The high efficiency of enzyme immobilization on chitosan beads indicates the suitability of this method for long-term storage of new lipase from native 5c isolate.