Fe(III) grafted MoO3 nanorods for effective electrocatalytic fixation of atmospheric N2 to NH3

Electrocatalytic nitrogen reduction reaction (ENRR) offers a carbon-neutral process to fix nitrogen into ammonia, but its feasibility depends on the development of highly efficient electrocatalysts. Herein, we report that Fe ion grafted on MoO₃ nanorods synthesized by an impregnation technique can efficiently enhance the electron harvesting ability and the selectivity of H⁺ during the NRR process in neutral electrolyte. In 0.1 M Na₂SO₄ solution, the electrocatalyst exhibited a remarkable NRR activity with an NH₃ yield of 9.66 μg h^?1 mg^?1_cat and a Faradaic efficiency (FE) of 13.1%, far outperforming the ungrafted MnO₃. Density functional theory calculations revealed that the Fe sites are major activation centers along the alternating pathway.     

Density functional theory study of the hydrogen evolution reaction in haeckelite boron nitride quantum dots

To satisfy arising energy needs and to handle the forthcoming worldwide climate transformation, the major research attention has been drawn to environmentally friendly, renewable and abundant energy resources. Hydrogen plays an ideal and significant role is such resources, due to its non-carbon based energy and production through clean energy. In this work, we have explored catalytic activity of a newly predicted haeckelite boron nitride quantum dot (haeck-BNQD), constructed from the infinite BN sheet, for its utilization in hydrogen production. Density functional theory calculations are employed to investigate geometry optimization, electronic and adsorption mechanism of haeck-BNQD using Gaussian16 package, employing the hybrid B3LYP and wB97XD functionals, along with 6–31G(d,p) basis set. A number of physical quantities such as HOMO/LUMO energies, density of states, hydrogen atom adsorption energies, Mulliken populations, Gibbs free energy, work functions, overpotentials, etc., have been computed and analysed in the context of the catalytic performance of haeck-BNQD for the hydrogen-evolution reaction (HER). Based on our calculations, we predict that the best catalytic performance will be obtained for H adsorption on top of the squares or the octagons of haeck-BNQD. We hope that our prediction of most active catalytic sites on haeck-BNQD for HER will be put to test in future experiments.     

Engineering the hydrogen storage properties of the perovskite hydride ZrNiH3 by uniaxial/biaxial strain

In the present work, the bonding length, electronic structure, stability, and dehydrogenation properties of the Perovskite-type ZrNiH₃ hydride, under different uniaxial/biaxial strains are investigated through ab-initio calculations based on the plane-wave pseudo-potential (PW-PP) approach. The findings reveal that the uniaxial/biaxial compressive and tensile strains are responsible for the structural deformation of the ZrNiH₃ crystal structure, and its lattice deformation becomes more significant with decreasing or increasing the strain magnitude. Due to the strain energy contribution, the uniaxial/biaxial strain not only lowers the stability of ZrNiH₃ but also decreases considerably the dehydrogenation enthalpy and decomposition temperature. Precisely, the formation enthalpy and decomposition temperature are reduced from ?67.73 kJ/mol.H₂ and 521 K for non-strained ZrNiH₃ up to ?33.73 kJ/mol.H₂ and 259.5 K under maximal biaxial compression strain of ε = ?6%, and to ?50.99 kJ/mol.H₂ and 392.23 K for the maximal biaxial tensile strain of ε = +6%. The same phenomenon has been also observed for the uniaxial strain, where the formation enthalpy and decomposition temperature are both decreased to ?39.36 kJ/mol.H₂ and 302.78 K for a maximal uniaxial compressive strain of ε = - 12%, and to ?51.86 kJ/mol.H₂ and 399 K under the maximal uniaxial tensile strain of ε = +12%. Moreover, the densities of states analysis suggests that the strain-induced variation in the dehydrogenation and structural properties of ZrNiH₃ are strongly related to the Fermi level value of total densities of states. These ab-initio calculations demonstrate insightful novel approach into the development of Zr-based intermetallic hydrides for hydrogen storage practical applications.     

Carbon corrosion mechanism on nitrogen-doped carbon support — A density functional theory study

In this work, density functional theory (DFT) calculations were used to investigate the mechanism of carbon corrosion on nitrogen-doped carbon support. Free energy diagrams were generated based on three proposed reaction pathways to evaluate corrosion mechanisms. The most energetically preferred mechanism on nitrogen-doped carbon was determined. The results show that the step of water dissociation to form ^#OH was the rate-determining step for gra-G-1N (graphene doped with graphitic N) and pyrr-G-1N (graphene doped with pyrrolic N). As for graphene doped with pyridinic N, the step of C^#OC^#O formation was critical. It was found that the control of nitrogen concentration was necessary for precisely designing optimized carbon materials. Abundance of nitrogen moieties aggravated the carbon corrosion. When the high potential was applied, specific types of graphitic N and pyridinic N were found to be favorable carbon modifications to improve carbon corrosion resistance. Moreover, the solvent effect was also investigated. The results provide theoretical insights and design guidelines to improve corrosion resistance in carbon support through material modification by inhibiting the adsorption of surface oxides (OH, O, and OOH).     

Lithiation MXene Derivative Skeletons for Wide-Temperature Lithium Metal Anodes

Lithium (Li) metal, as an appealing candidate for the next-generation of high-energy-density batteries, is plagued by its safety issue mainly caused by uncontrolled dendrite growth and infinite volume expansion. Developing new materials that can improve the performance of Li-metal anode is one of the urgent tasks. Herein, a new MXene derivative containing pure rutile TiO₂ and N-doped carbon prepared by heat-treating MXene under a mixing gas, exhibiting high chemical activity in molten Li, is reported. The lithiation MXene derivative with a hybrid of LiTiO₂-Li₃N-C and Li offers outstanding electrochemical properties. The symmetrical cell assembling lithiation MXene derivative hybrid anode exhibits an ultra-long cycle lifespan of 2000 h with an overpotential of ≈30 mV at 1 mA cm⁻², which overwhelms Li-based anodes reported so far. Additionally, long-term operations of 34, 350, and 500 h at 10 mA cm⁻² can be achieved in symmetrical cells at temperatures of −10, 25, and 50 °C, respectively. Both experimental tests and density functional theory calculations confirm that the LiTiO₂-Li₃N-C skeleton serves as a promising host for Li infusion by alleviating volume variation. Simultaneously, the superlithiophilic interphase of Li₃N guides Li deposition along the LiTiO₂-Li₃N-C skeleton to avoid dendrite growth.     

Thermal desorption and pyrolysis direct analysis in real time mass spectrometry of Nafion membrane

Perfluorosulfonic acid ionomer membranes have been widely used as proton conducting membranes in various electrochemical processes such as polymer electrolyte fuel cells and water electrolysis. While their thermal stability has been studied by thermogravimetry and analysis of low molecular weight products, their decomposition mechanism is little understood. In this study a newly developed methodology of thermal desorption and pyrolysis in combination with direct analysis in real time mass spectrometry is applied for Nafion membrane. An ambient ionization source and a high-resolution time-of-flight mass spectrometer enabled unambiguous assignment of gaseous products. Thermal decomposition is initiated by side chain detachment above 350°C, which leaves carbonyls on the main chain at the locations of the side chains. Perfluoroalkanes are released above 400°C by main chain scission and their further decomposition products dominate above 500 °C. DFT calculation of reaction energies and barrier heights of model compounds support proposed decomposition reactions.     

Secure image encryption scheme using 4D-Hyperchaotic systems based reconfigurable pseudo-random number generator and S-Box

This paper introduces the design of a hardware efficient reconfigurable pseudorandom number generator (PRNG) using two different feedback controllers based four-dimensional (4D) hyperchaotic systems i.e. Hyperchaotic-1 and -2 to provide confidentiality for digital images. The parameter's value of these two hyperchaotic systems is set to be a specific value to get the benefits i.e. all the multiplications (except a few multiplications) are performed using hardwired shifting operations rather than the binary multiplications, which doesn't utilize any hardware resource. The ordinary differential equations (ODEs) of these two systems have been exploited to build a generic architecture that fits in a single architecture. The proposed architecture provides an opportunity to switch between two different 4D hyperchaotic systems depending on the required behavior. To ensure the security strength, that can be also used in the encryption process in which encrypt the input data up to two times successively, each time using a different PRNG configuration. The proposed reconfigurable PRNG has been designed using Verilog HDL, synthesized on the Xilinx tool using the Virtex-5 (XC5VLX50T) and Zynq (XC7Z045) FPGA, its analysis has been done using Matlab tool. It has been found that the proposed architecture of PRNG has the best hardware performance and good statistical properties as it passes all fifteen NIST statistical benchmark tests while it can operate at 79.101-MHz or 1898.424-Mbps and utilize only 0.036 %, 0.23 %, and 1.77 % from the Zynq (XC7Z045) FPGA's slice registers, slice LUTs, and DSP blocks respectively. Utilizing these PRNGs, we design two 16 × 16 substitution boxes (S-boxes). The proposed S-boxes fulfill the following criteria: Bijective, Balanced, Non-linearity, Dynamic Distance, Strict Avalanche Criterion (SAC) and BIC non-linearity criterion. To demonstrate these PRNGs and S-boxes, a new three different scheme of image encryption algorithms have been developed: a) Encryption using S-box-1, b) Encryption using S-box-2 and, c) Two times encryption using S-box-1 and S-box-2. To demonstrate that the proposed cryptosystem is highly secure, we perform the security analysis (in terms of the correlation coefficient, key space, NPCR, UACI, information entropy and image encryption quantitatively in terms of (MSE, PSNR and SSIM)).     

An industrial case study on variability handling in large enterprise software systems

ContextEnterprise software systems (e.g., enterprise resource planning software) are often deployed in different contexts (e.g., different organizations or different business units or branches of one organization). However, even though organizations, business units or branches have the same or similar business goals, they may differ in how they achieve these goals. Thus, many enterprise software systems are subject to variability and adapted depending on the context in which they are used.ObjectiveOur goal is to provide a snapshot of variability in large scale enterprise software systems. We aim at understanding the types of variability that occur in large industrial enterprise software systems. Furthermore, we aim at identifying how variability is handled in such systems.MethodWe performed an exploratory case study in two large software organizations, involving two large enterprise software systems. Data were collected through interviews and document analysis. Data were analyzed following a grounded theory approach.ResultsWe identified seven types of variability (e.g., functionality, infrastructure) and eight mechanisms to handle variability (e.g., add-ons, code switches).ConclusionsWe provide generic types for classifying variability in enterprise software systems, and reusable mechanisms for handling such variability. Some variability types and handling mechanisms for enterprise software systems found in the real world extend existing concepts and theories. Others confirm findings from previous research literature on variability in software in general and are therefore not specific to enterprise software systems. Our findings also offer a theoretical foundation for describing variability handling in practice. Future work needs to provide more evaluations of the theoretical foundations, and refine variability handling mechanisms into more detailed practices.     

Sustainability of ride-hailing services in China’s mobility market: A simulation model of socio-technical system transition

As a symbol of sharing economy, ride-hailing services have spread to Asia, where various forms of services have been established according to the existing socio-technical regimes, including legal, policy, and environmental concerns. China, in particular, has accepted ride-hailing services by revising existing institutions. This study analyzes China’s acceptance of ride-hailing services in the socio-technical system context set up for legacy services. Simulation modeling, combined with transition theory and an agent-based model, is used to analyze the data. This study calculates consumer disutility based on mobility market share, reflecting consumer preference, and predicts the sustainability of ride-hailing services. The simulation results conclude that legalization and socio-technical context are of importance for sustainable mobility.     

Parallel chaos optimization algorithm with migration and merging operation

Chaos optimization algorithm (COA) utilizes the chaotic maps to generate the pseudo-random sequences mapped as the decision variables for global optimization applications. A kind of parallel chaos optimization algorithm (PCOA) has been proposed in our former studies to improve COA. The salient feature of PCOA lies in its pseudo-parallel mechanism. However, all individuals in the PCOA search independently without utilizing the fitness and diversity information of the population. In view of the limitation of PCOA, a novel PCOA with migration and merging operation (denoted as MMO-PCOA) is proposed in this paper. Specifically, parallel individuals are randomly selected to be conducted migration and merging operation with the so far parallel solutions. Both migration and merging operation exchange information within population and produce new candidate individuals, which are different from those generated by stochastic chaotic sequences. Consequently, a good balance between exploration and exploitation can be achieved in the MMO-PCOA. The impacts of different one-dimensional maps and parallel numbers on the MMO-PCOA are also discussed. Benchmark functions and parameter identification problems are used to test the performance of the MMO-PCOA. Simulation results, compared with other optimization algorithms, show the superiority of the proposed MMO-PCOA algorithm.