Enhanced graphitic domains of unreduced graphene oxide and the interplay of hydration behaviour and catalytic activity

Previous studies indicate that the properties of graphene oxide (GO) can be significantly improved by enhancing its graphitic domain size through thermal diffusion and clustering of functional groups. Remarkably, this transition takes place below the decomposition temperature of the functional groups and thus allows fine tuning of graphitic domains without compromising with the functionality of GO. By studying the transformation of GO under mild thermal treatment, we directly observe this size enhancement of graphitic domains from originally ≤40 nm² to >200 nm² through an extensive transmission electron microscopy (TEM) study. Additionally, we confirm the integrity of the functional groups during this process by a comprehensive chemical analysis. A closer look into the process confirms the theoretical predicted relevance for the room temperature stability of GO and the development of the composition of functional groups is explained with reaction pathways from theoretical calculations. We further investigate the influence of enlarged graphitic domains on the hydration behaviour of GO and the catalytic performance of single atom catalysts supported by GO. Additionally, we show that the sheet resistance of GO is reduced by several orders of magnitude during the mild thermal annealing process.     

A software tool for translating deterministic model results into probabilistic assessments of water quality standard compliance

Most assessments of whether a water body will comply with pollutant standards after modification of land use, loading, or climate change are based on the results of deterministic simulation models. These models, including those used to support the United States Environmental Protection Agency (USEPA) total maximum daily load (TMDL) program, typically do not account for common sources of assessment uncertainty. Instead, model results are typically represented by a time series of predicted pollutant concentration values or the parameters of a frequency-based distribution of these values over a specified time period. The rate of exceedance of relevant pollutant limits is then assessed directly from this time series or distribution to determine standard compliance. In this way, sampling and analysis-based variability and model uncertainty are typically ignored, although they may substantially influence the probability of non-compliance. To help address this problem, we introduce ProVAsT (Probabilistic Water Quality Standard Violation Assessment Tool), a software tool encoded in the graphical model-based package Analytica^®. Here, we present a version of ProVAsT which translates model-predicted in situ fecal indicator bacteria (FIB) pollutant concentrations into the expected frequency of water quality standard violations and provides a Bayesian measure of the degree of confidence in this assessment. We call this version ProVAsT-FIB. Along with inputting their own simulation model results, users can specify the particular water quality analysis methods employed (e.g. the analytic procedure used and the number and volume of sample aliquots) as well as the numeric limits pertaining to local water quality standards. It is our hope that ProVAsT will encourage the rational consideration of uncertainty and variability in water quality assessments by reducing the burden of complex statistical calculations.     

Synthesis,crystal structure,luminescence and thermal behavior of a new energetic zinc(II) compound

An energetic material [Zn₂(btzphda)₂(H₂O)₄(dpp)₂]·2DMF·4H₂O with high decomposition enthalpy of − 748.35 J/g was prepared by the reaction of H₂btzphda, dpp and Zn(NO₃)₂·6H₂O under solvothermal conditions, where btzphda = 1,4-bis(tetrazol-5-yl)benzene-N2,N2′-diacetato, dpp = 1.3-di(4-pyridyl)propane and DMF = N,N′-dimethylformamide. The luminescence properties of H₂btzphda and [Zn₂(btzphda)₂(H₂O)₄(dpp)₂]·2DMF·4H₂O were investigated at room temperature in the solid state (Hitachi F4600 spectrofluorometer). Furthermore, the thermal decomposition behavior of the compound is characterized by differential scanning calorimetry (DSC) and thermogravimetric-differential thermogravimetric (TG-DTG) analyses. The entropy of activation (ΔH), enthalpy of activation (ΔS) and the free energy of activation (ΔG) for the decomposition temperature were ΔH = 250.64 kJ/mol, ΔS = 222.75 J·mol^− 1·K^− 1 and ΔG = 134.10 kJ/mol.     

Delivering cloud services with QoS requirements: Business opportunities,architectural solutions and energy-saving aspects

The flexible and pay-as-you-go computing capabilities offered by Cloud infrastructures are nowadays very attractive, and widely adopted by many organizations and enterprises. In particular this is true for those having periodical or variable tasks to execute, and, choose to not or cannot afford the expenses of buying and managing computing facilities or software packages, that should remain underutilized for most of the time. For their ability to couple the scalability offered by public service providers, with the wider Quality of Service (QoS) provisions and ad-hoc customizations provided by private Clouds, Hybrid Clouds (HC) seem a particularly appealing solution for customers requiring something more than the mere availability of the service.The paper firstly introduces a Cloud brokering system leveraging on a promising architectural approach, based on the use of a gateway toolkit. This approach provides noticeably advantages, both to customers and to Cloud Brokers (CB), for its ability to hide all the intricacies related to the management of powerful, but often complex and heterogeneous infrastructures like the Cloud. Moreover such approach, through customized interfaces, facilitates customers in accessing Cloud resources thus easing the tailored deployment and execution of their applications and workflows.The major contribution of this work is given by the analysis of a set of brokering strategies for Hybrid Clouds, implemented by a brokering algorithm, aimed at the execution of various applications subject to different user requirements and computational conditions. With the objective of firstly maximize both user satisfaction and CB’s revenues the algorithm also pursues profit increases through the reduction of energy costs by adopting energy saving mechanisms. A simulation model is used to evaluate performance, and the results show that differences among strategies depend on type and size of system loads and that the use of turn on and off techniques greatly improves energy savings at low and medium load rates thus indirectly increasing CB revenues without diminishing customers’ satisfaction.     

Protium removal from deuterium-tritium mixture with displacement chromatography method: Experiments and simulations

The displacement chromatography technique with a tri-column system was used to reduce the protium (H) in the deuterium-tritium (D-T) mixture, and the separation performance was studied numerically by ANSYS FLUENT. The experimental results showed that the isotopic abundance of H in the D-T mixture dropped from 2.7% to an acceptable level of 0.88%. The simulation results showed that a lower porosity (θ) of the filling material made a higher separation factor, but a lower separation efficiency. The velocity of the product gas at the outlet of the separation column approximately had a linear relationship with θ^5/3/(1-θ)², which partly indicated the pore diffusion resistance. The mixed gas could contact the filling materials more sufficiently under a lower flow rate resulting in a lower protium concentration in the product gas. The separation column with a thin and long shape had a better separation performance and a lower product gas loss.     

Promoting effects of pretreatment on Pd/CeO2 catalysts for CO oxidation

CeO₂ supported Pd catalysts were prepared in which the Pd species were presented in form of PdO and Ce_1-xPd_xO_2-δ solid solution. The Pd/CeO₂ catalysts were thermal treated for varying duration and its effect on Pd species was explored. The transformation of Pd species and redispersion were observed under oxidizing conditions at 500 °C. For catalyst treated with 10 h, more Pd ions penetrated into the CeO₂ matrix to form Ce_1-xPd_xO_2-δ solid solution, resulting in a 90% CO conversion at 84 °C after H₂ reduction. Another thermal treatment time extension led to an extraction of Pd from CeO₂ lattice in tandem with higher dispersion and smaller PdO particles on the surface, which was demonstrated by the results of XRD, ICP, TEM images, CO pulse adsorption and CO-TPR as a redispersion phenomenon.     

Upgrading the lubricity of bio-oil via homogeneous catalytic esterification under vacuum distillation conditions

In order to accelerate the application of bio-oil in the internal combustion engines, homogeneous catalytic esterification technology under vacuum distillation conditions was used to upgrade the crude bio-oil. The lubricities of the crude bio-oil (BO) and refined bio-oil with homogeneous catalytic esterification (RBO_hce) or refined bio-oil without catalyst but with distillation operation (RBO_wc) were evaluated by a high frequency reciprocating test rig according to the ASTM D 6079 standard. The basic physiochemical properties and components of the bio-oils were analyzed. The surface morphology, contents and chemical valence of active elements on the worn surfaces were investigated by scanning electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy, respectively. The results show that RBO_hce has better lubricities than those of BO, but RBO_wc has worse lubricities than those of BO. The tribological mechanisms of the bio-oils are attributed to the combined actions of lubricating films and factors that will break the film. Compared with BO, plenty of phenols in RBO_wc results in corrosion of the substrate and destroys the integrity of the lubricating films, which is responsible for its corrosive wear. However, more esters and alkanes in RBO_hce contribute to forming a complete boundary lubricating film on the rubbed surfaces which result in its excellent antifriction and antiwear properties.     

Crystal field of rare earth impurities in LaF3

The crystal field parameters of 13 trivalent lanthanide ions substituted for La in LaF₃ were calculated using the combination of the band structure and Wannier function calculations. Performing an atomic exact diagonalization with thus obtained crystal-field parameters we compute the crystal-field splitting of atomic multiplets. The calculation is compared with the available experimental results and a good agreement is found.     

A new cadmium-organic framework fluorescent sensor for Al3 + and Ca2 + ions in aqueous medium

A new metal-organic framework (MOF), [Cd₂(bptc)(HCOO)]·NH₂(CH₃)₂·3H₂O (1), where H₄bptc = 3,3′,5,5′-biphenyltetracarboxylic acid, was obtained by solvothermal reaction. The topology of MOF 1 is a (5,8)-connected net with {4¹⁶ · 5⁸ · 6⁴}{4⁴ · 5⁶}₂ point symbol. MOF 1 shows high stability in aqueous solution. Luminescence study indicates that MOF 1 possesses selective turn-on luminescent sensing functions towards Al^3 + and Ca^2 + ions in aqueous solutions.     

CeF3-modified LiNi1/3Co1/3Mn1/3O2 cathode material for high-voltage Li-ion batteries

A facile chemical deposition method has been adopted to prepare cerium fluoride (CeF₃) surface modified LiNi_1/3Co_1/3Mn_1/3O₂ as cathode material for lithium-ion batteries. Structure analyses reveal that the surface of LiNi_1/3Co_1/3Mn_1/3O₂ particles is uniformly coated by CeF₃. Electrochemical tests indicate that the optimal CeF₃ content is 1 wt%. The 1 wt% CeF₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ can deliver a discharge capacity of 107.1 mA h g⁻¹ even at 5 C rate, while the pristine does only 57.3 mA h g⁻¹. Compared to the pristine, the 1 wt% CeF₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ exhibits the greatly enhanced capacity and cycling stability in the voltage range of 3.0–4.5 V, which suggests that the CeF₃ coating has the positive effect on the high-voltage application of LiNi_1/3Co_1/3Mn_1/3O₂. According to the analyses from electrochemical impedance spectra, enhanced electrochemical performance is mainly because the stable CeF₃ coating layer can prevent the HF-containing electrolyte from continuously attacking the LiNi_1/3Co_1/3Mn_1/3O₂ cathode and retard the passivating layer growth on the cathode.