Hybrid density functional∕molecular mechanics studies on activated adsorption of oxygen on zeolite supported gold monomer

Density functional theory calculations on oxygen adsorption over gas phase and faujasite supported Au monomer has been studied using hybrid quantum mechanics∕molecular mechanics method, surface integrated molecular orbital molecular mechanics implemented in GAMESS package. Three different oxidation states of Au (0, +1, +3) and three different adsorption modes viz., top, bridge, and dissociative adsorption of oxygen have been considered in our calculations. Redshift in the ν(O-O) value from that in gas phase O(2) indicates activation of O(2) upon adsorption over faujasite supported gold monomer. The activation of O(2) is an important step in the catalytic oxidation of CO. The presence of adsorbed O(2) increases the interaction of the Au monomer with the faujasite support. In faujasite supported cationic Au monomer, O(2) preferably remains bridge bonded to Au rather than being dissociated.     

A molecular simulation study of the distribution of cation in zeolites

NVT Monte Carlo simulations are first used to describe the distribution of Na cations in Faujasite for several Si/Al ratios. These calculations were performed by combining two different sets of potential parameters combined with both T-atoms and explicit Si,Al models. Grand Canonical Monte Carlo simulations are then employed to investigate the influence of water adsorption on the distribution of cations in the case of a Faujasite sample with 56 cations (NaY56). These simulations data are compared to available experimental data and the influence of the choice of the forcefield for describing the cation/zeolite interaction on these results is discussed.     

Capture of CO2 from flue gas streams with zeolite 13X by vacuum-pressure swing adsorption

Vacuum swing adsorption (VSA) capture of CO₂ from flue gas streams is a promising technology for greenhouse gas mitigation. In this study we use a detailed, validated numerical model of the CO2VSA process to study the effect of a range of operating and design parameters on the system performance. The adsorbent used is 13X and a feed stream of 12% CO₂ and dry air is used to mimic flue gas. Feed pressures of 1.2 bar are used to minimize flue gas compression. A 9-step cycle with two equalisations and a 12-step cycle including product purge were both used to understand the impact of several cycle changes on performance. The ultimate vacuum level used is one of the most important parameters in dictating CO₂ purity, recovery and power consumption. For vacuum levels of 4 kPa and lower, CO₂ purities of >90% are achievable with a recovery of greater than 70%. Both purity and recovery drop quickly as the vacuum level is raised to 10 kPa. Total power consumption decreases as the vacuum pressure is raised, as expected, but the recovery decreases even quicker leading to a net increase in the specific power. The specific power appears to minimize at a vacuum pressure of approximately 4 kPa for the operating conditions used in our study. In addition to the ultimate vacuum level, vacuum time and feed time are found to impact the results for differing reasons. Longer evacuation times (to the same pressure level) imply lower flow rates and less pressure drop providing improved performance. Longer feed times led to partial breakthrough of the CO₂ front and reduced recovery but improved purity. The starting pressure of evacuation (which is not necessarily equal to the feed pressure) was also found to be important since the gas phase was enriched in CO₂ prior to removal by vacuum leading to improved CO₂ purity. A 12-step cycle including product purge was able to produce high purity CO₂ (>95%) with minimal impact on recovery. Finally, it was found that for 13X, the optimal feed temperature was around 67°C to maximize system purity. This is a consequence of the temperature dependence of the working selectivity and working capacity of 13X. In summary, our numerical model indicates that there is considerable scope for improvement and use of the VSA process for CO₂ capture from flue gas streams.     

Prediction of competitive adsorption on coal by a lattice DFT model

Adsorption is one of the main mechanisms involved in the ECBM process, a technology where CO₂ (or flue gas, i.e. a CO₂/N₂ mixture) is injected into a deep coal bed, with the aim of storing CO₂ by simultaneously recovering CH₄. A detailed understanding of the microscopic adsorption process is therefore needed, as the latter controls the displacement process. A lattice DFT model, previously extended to mixtures, has been applied to predict the competitive adsorption behavior of CO₂, CH₄ and N₂ and of their mixtures in slit-shaped pores of 1.2 and 8 nm width. In particular, the effect of temperature, bulk composition and density on the resulting lattice pore profiles and on the lattice excess adsorption isotherms has been investigated. Important insights could be obtained; when approaching near critical conditions in the mesopores, a characteristic peak in the excess adsorption isotherm of CO₂ appears. The same effect could be observed neither for the other gases nor in the micropores. Moreover, in the case of mixtures, a depletion of the less adsorbed species close to the adsorbent surface is observed, which eventually results in negative lattice excess adsorption at high bulk densities.     

Study on multimers and their structures in molecular association mixture

Self-association system of(R)-1,3-butanediol in dilute carbon tetrachloride(CCl4)solution is studied as a model of molecular association mixture.Analysis methods including FSMWEFA(fixed-size moving window evolving factor analysis)combined with PCA(principal component analysis),SIMPLISMA (simple-to-use interactive self-modeling mixture analysis),and ITTFA(iterative target transformation factor analysis)are adopted to resolve infrared spectra of(R)-1,3-butanediol solution.Association number and equilibrium constant are computed.(R)-1,3-butanediol in dilute inert solution is determined as a monomer-trimer equilibrium system.Theoretical investigation of trimer structures is carried out with DFT(density functional theory),and structural factors are analyzed.     

Capture of CO2 from high humidity flue gas by vacuum swing adsorption with zeolite 13X

Capture of CO₂ from flue gas streams using adsorption processes must deal with the prospect of high humidity streams containing bulk CO₂ as well as other impurities such as SO _x , NO _x , etc. Most studies to date have ignored this aspect of CO₂ capture. In this study, we have experimentally examined the capture of CO₂ from a 12% synthetic flue gas stream at a relative humidity of 95% at 30 °C. A 13X adsorbent was used and the migration of the water and its subsequent impact on capture performance was evaluated. Binary breakthrough of CO₂/water vapor was performed and indicated a significant effect of water on CO₂ adsorption capacity, as expected. Cyclic experiments indicate that the water zone migrates a quarter of the way into the column and stabilizes its position so that CO₂ capture is still possible although decreased. The formation of a water zone creates a “cold spot” which has implications for the system performance. The recovery of CO₂ dropped from 78.5% to 60% when moving from dry to wet flue gas while the productivity dropped by 22%. Although the concentration of water leaving the bed under vacuum was 27%(vol), the low vacuum pressure prevented condensation of water in this stream. However, the vacuum pump acted as a condenser and separator to remove bulk water. An important consequence of the presence of a water zone was to elevate the vacuum level thereby reducing CO₂ working capacity. Thus although there is a detrimental effect of water on CO₂ capture, long term recovery of CO₂ is still possible in a single VSA process. Pre-drying of the flue gas steam is not required. However, careful consideration of the impact of water and accommodation thereof must be made particularly when the feed stream temperature increases resulting in higher feed water concentration.     

Study on preparation and visible-light activity of Ag–TiO2 supported by artificial zeolite

Research on Chemical Intermediates - The material of Ag–TiO2 supported by artificial zeolite (Ag–TiO2/Z) was synthesized by the sol–gel method. Tetrabutyl titanate was used as the...     

Study on the Interaction of Pentachlorophenol with Urease in Aqueous Solution by Multiple Spectroscopic Techniques

The interactions between pentachlorophenol (PCP) and jack bean urease were studied using UV/vis absorption, CD, fluorescence, synchronous fluorescence, and three-dimensional fluorescence spectroscopic techniques. The fluorescence data showed that the fluorescence quenching of urease by PCP the results of the formation of a PCP–urease complex involving a hydrophobic interaction. The distance r between the donor (urease) and acceptor (PCP) was obtained from the fluorescence resonance energy transfer. The effect of PCP on the conformation of urease was analyzed using UV/vis absorption, synchronous fluorescence and three-dimensional fluorescence spectroscopic techniques. The result showed that PCP can enter into the hydrophobic pocket at the interface of urease and that the micro environments around the tyrosine and tryptophan residues were changed.     

Study on the Synergism Effect of Lomefloxacin and Ofloxacin for Bovine Serum Albumin in Solution by Spectroscopic Techniques

Both lomefloxacin (LOM) and ofloxacin (OFL) have a powerful ability to quench the fluorescence of bovine serum albumin (BSA). The fluorescence quenching action is much stronger when the two drugs coexist. The synergism between LOM and OFL was studied using fluorescence and ultraviolet spectroscopy under imitated physiological conditions. The results show that static quenching and non-radiation energy transfer are the main reasons for the fluorescence quenching. The synergism results in both the reduction of the binding stability between drugs and BSA and an increase of the free drug concentration, which will increase the efficacy of drugs. The thermodynamic parameters at different temperatures were calculated and the binding distances r between the drugs and BSA were obtained based on Försters theory of non-radiation energy transfer. The synchronous fluorescence spectra indicated that the effect of synergism affected the conformation of BSA.     

Bioreduction of quinone derivatives by immobilized Baker''''s yeast in hexane

Immobilization techniques and biocatalytic transformations performed in organic media are new developing methods for organic reactions. Baker's yeast was immobilized on the alginate supports. This preparation contained about 20% of dry yeast cells. The immobilized Baker's yeast were found to be very effective in the reduction of o-benzoquinone, p-benzoquinones, naphthoquinones, and anthraquinones in hexane.     

Study on the Inhibition of Mild Steel Corrosion by Cationic Gemini Surfactant in 1 M HCl

The cationic gemini surfactant 1,2-bis(N-tetradecyl-N,N-dimethylammonium)ethane dibromide (14-2-14) was synthesized using a previously described method. The surfactant was characterized using ¹H NMR. The corrosion inhibition effect of 14-2-14 on mild steel in 1 M HCl at temperatures 30–60°C was studied using weight loss measurements, potentiodynamic polarization measurements and electrochemical impedance spectroscopy. Morphology of the corroded mild steel specimens was examined using scanning electron microscopy (SEM). The results of the studies show that gemini surfactant is an efficient inhibitor for mild steel corrosion in 1 M HCl; the maximum inhibition efficiency (IE) of 98.06% is observed at surfactant concentration of 100 ppm at 60°C. The %IE increases with the increasing inhibitor concentration and temperature. The adsorption of inhibitor on the mild steel surface obeys Langmuir adsorption isotherm. SEM studies confirmed smoother surface for inhibited mild steel specimen.     

Study on the interaction between baicalein and the amyloid β peptide by molecular spectroscopy

The amyloid β peptide (Aβ) is the major protein constituent of neuritic plaques in Alzheimer's disease (AD).And Aβ(1-42) is the major component in amyloid plaque core deposits.     

Study of Brønsted acid site in H-MCM-22 zeolite by temperature-programmed desorption of ammonia

Interaction of ammonia with H-MCM-22 zeolite (Si/Al = 24.5) was investigated by temperature-programmed desorption technique in order to obtain information on thermodynamics of the process. Average activation energy for desorption of ammonia from Brønsted acid sites of H-MCM-22 zeolite was estimated from the data obtained under conditions varying in heating rate and also flow rate of carrier gas. It resulted in value of E _d = 127 kJ mol^?1 for heat rate variation method, whereas flow rate variation led to E _d value of 111 kJ mol^?1. Obtained E _d values are compared with those reported in the literature for other zeolitic materials and discussed in the broader context of zeolite acidity. Comparison of E _d values estimated here for H-MCM-22 zeolite with corresponding data for other protonic zeolites shows that H-MCM-22 displays mediocre/lower activation energy for ammonia compared with other high-silica zeolites.     

Structural analysis of polymer-brush-type cellulose β-ketoesters by molecular dynamics simulation

The reason for anomalous NMR patterns of cellulose β-ketoesters, which were prepared by reaction between cellulose and ketene dimers having long alkyl chains (AKDs) under homogeneous conditions using a cellulose solvent system, was studied by molecular dynamics simulation. Cellulose/AKD β-ketoester models with degree of substitution (DS) 2.0 and degree of polymerization (DP) 5, 10, 20 or 40, and cellulose/fatty acid ester models with DS 3.0 and DP 5, 10, 20 or 40 were assembled in the simulation. The calculated results were compared with those obtained by NMR and conformation analyses of the actually prepared cellulose derivatives. The molecular dynamics simulation data showed that the average velocities of anhydroglucose units in cellulose/AKD β-ketoesters were approximately one tenth of those in cellulose/fatty acid esters. Thus, cellulose chains in the cellulose/AKD β-ketoesters are extremely restricted in motion by the β-ketoester substituents. The solid-like behavior of cellulose chains in cellulose/AKD β-ketoesters in solution state is, therefore, explainable by strong restriction in motion of cellulose chains by long, branched and bulky substituents introduced into cellulose hydroxyls in high densities via β-ketoester bonds.     

Hydrogen separation by multi-bed pressure swing adsorption of synthesis gas

The performance of multi-bed pressure swing adsorption (PSA) process for producing high purity hydrogen from synthesis gas was studied experimentally and theoretically using layered beds of activated carbon and zeolite 5A. Nonisothermal and nonadiabatic models, considering linear driving force model and Dual-site Langmuir adsorption isotherm model, were used. The effects of the following PSA variables on separation process were investigated: linear velocity of feed, adsorption time and purge gas quantity. As a result, we recovered a high purity H₂ product (99.999%) with a recovery of 66% from synthesis gas when the pressure was cycled between 1 and 8 atm at ambient temperature.     

Tensile strength of Iβ crystalline cellulose predicted by molecular dynamics simulation

The mechanical properties of Iβ crystalline cellulose are studied using molecular dynamics simulation. A model Iβ crystal is deformed in the three orthogonal directions at three different strain rates. The stress–strain behaviors for each case are analyzed and then used to calculate mechanical properties. The results show that the elastic modulus, Poisson’s ratio, yield stress and strain, and ultimate stress and strain are highly anisotropic. In addition, while the properties that describe the elastic behavior of the material are independent of strain rate, the yield and ultimate properties increase with increasing strain rate. The deformation and failure modes associated with these properties and the relationships between the material’s response to tension and the evolution of the crystal structure are analyzed.     

Characterization of two single-wall carbon nanotubes samples by Ar and Kr adsorption isotherms

We investigated by Ar and Kr adsorption isotherm techniques for two kinds of carbon single-wall nanotube bundles prepared by different synthesis methods. Despite the difference in the adsorption capacity in the two samples, the adsorption mechanisms are similar, which indicates that the same adsorption sites are involved for Ar and Kr. We have already measured a similar difference in the adsorbed amount in these samples studied by a low-temperature heat-capacity technique, i.e., for the case of ⁴He as adsorbate. These results cannot be easily explained by only taking into account the topology of the bundles if all tubes are closed-ended. A larger spread of effective surface areas among different sources of samples is reported in the literature data.