Pt–Ru nanoparticles anchored on poly(brilliant cresyl blue) as a new polymeric support: Application as an efficient electrocatalyst in methanol oxidation reaction

The glassy carbon electrode is modified by poly(brilliant cresyl blue) (PBCB) to be applied as a new green and efficient platform for Pt and Pt–Ru alloy nanoparticles deposition. Surface composition, morphology and catalytic activity of these modified electrodes towards methanol oxidation are assessed by applying X-ray diffraction, field emission scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy techniques. The X-ray diffraction patterns reveal that the highly crystalline Pt and Pt–Ru alloy and RuO₂ nanoparticles with low crystallinity are deposited on the PBCB modified glassy carbon electrodes. The microscopic images indicate smaller size and better distribution of deposited nanoparticles on the surface of PBCB modified electrodes. Cyclic voltammetry and electrochemical impedance spectroscopy results reveal that PBCB supported Pt and Pt–Ru nanoparticles have better electrocatalytic performance and durability towards methanol oxidation rather than the unsupported nanoparticles. From the obtained results it can be concluded that the presence of PBCB not only improves the stability of nanoparticles on the surface, but also leads to the formation of smaller size and more uniform distribution of nanoparticles on the surface, which, in turn, cause the nanoparticles to provide a higher accessible surface area and more active centers for the oxidation of methanol. The results will be valuable in extending the applications of this polymer in surface modification steps and in developing promising catalyst supports to be applied in direct methanol fuel cells.     

Impact sensitivities of energetic materials: Exploring the limitations of a model based only on structural formulas

Using a comprehensive set of drop weight impact test data (h₅₀) newly compiled from literature for 308 materials, a recent approach to predict impact sensitivities of nitro compounds is generalized to most explosive substances of interest. Compared to previous ones, this procedure is more thoroughly validated and exhibits a good predictive value. Furthermore, it yields new insight into the physical mechanisms involved, explaining for instance the unexpected desensitization of some oxygen-deficient triazoles upon nitration.     

Polymer derived ceramic materials from Si,B and MoSiB filler-loaded perhydropolysilazane precursor for oxidation protection

Silica-based coating systems were developed using polymer derived ceramics (PDCs) technology. Ceramic composites on the base of a SiO₂ and SiNO matrix and homogeneously distributed Mo₅SiB₂, SiB₆, Si and B fillers were manufactured. The coating systems have low porosity and provide a high oxidation resistance up to 100 h at 800 °C and 1100 °C in air. The influence of temperature and atmosphere of pyrolysis on the polymer precursor, the volume fraction of filler materials on the chemical composition of compacts as well as their high-temperature oxidation protection was investigated.     

Homogenization with uncertainty in Poisson ratio for polymers with rubber particles

The main aim of this work is dual computer analysis of probabilistic coefficients for the homogenized tensor of the polymer filled with the rubber particles having randomized Poisson ratios of both constituents. The major issue is to verify an influence of a randomness in rubber Poisson ratio close to the compressibility limit on the uncertainty of the effective tensor probabilistic characteristics. Probabilistic analysis presented here is carried out using mainly the stochastic perturbation technique provided by the common application of the traditional FEM commercial code ABAQUS and the symbolic computations package MAPLE. This FEM-based technique employs polynomial response function of the optimum order recovered from the weighted least squares method and following a set of deterministic solutions obtained for various values of the randomized input parameter. Optimization procedure is released entirely into a symbolic environment, where maximization of the correlation factor together with minimization of the fitting variance and approximation error are applied. Homogenization technique consists in equating of deformation energies for the real composite and the artificial one characterized by the effective elasticity tensor with uncertainty.     

Ultrasmall rhodium nanoclusters anchored on nitrogen-doped carbon nanotubes with embedded nickel nanoparticles as magnetically recyclable catalysts for efficient ammonia-borane hydrolysis

Facile yet efficient synthesis of high-performance nanocatalysts for hydrogen evolution from ammonia-borane (AB) hydrolysis is paramount. Here, we reported a novel hybrid nanocatalyst comprised of Rh nanoclusters (1.56 nm in diameters) anchored on nitrogen (N)-doped carbon nanotubes with embedded Ni nanoparticles (Ni@NCNTs), which was fabricated through adsorption of Rh ions on Ni@NCNTs. The achieved hybrid of Rh/Ni@NCNTs displayed excellent catalytic property (Turnover frequency: 959 min⁻¹) toward AB hydrolysis, higher than many prior developed Rh-based catalysts. Note that this hybrid could be reused for at least nine runs with complete AB conversion to hydrogen. Rh nanoclusters with small size exhibiting high atom utilization and the synergetic effect between Ni and Rh are responsible for the excellent catalytic property of Rh/Ni@NCNTs toward AB hydrolysis. This work highlights the importance of utilization of magnetically recyclable Ni@NCNTs as support and synergetic component for efficient hydrolysis of AB.     

Cost-minimization analysis of a working vacation queue with N-policy and server breakdowns

This paper investigates the N-policy M/M/1 queueing system with working vacation and server breakdowns. As soon as the system becomes empty, the server begins a working vacation. The server works at a lower service rate rather than completely stopping service during a vacation period. The server may break down with different breakdown rates during the idle, working vacation, and normal busy periods. It is assumed that service times, vacation times, and repair times are all exponentially distributed. We analyze this queueing model as a quasi-birth–death process. Furthermore, the equilibrium condition of the system is derived for the steady state. Using the matrix-geometric method, we find the matrix-form expressions for the stationary probability distribution of the number of customers in the system and system performance measures. The expected cost function per unit time is constructed to determine the optimal values of the system decision variables, including the threshold N and mean service rates. We employ the particle swarm optimization algorithm to solve the optimization problem. Finally, numerical results are provided, and an application example is given to demonstrate the applicability of the queueing model.     

Using d-limonene as the non-aromatic and non-chlorinated solvent for the fabrications of high performance polymer light-emitting diodes and field-effect transistors

Aiming to environment protection, green solvents are crucial for commercialization of solution-processed optoelectronic devices. In this work, d-limonene, a natural product, was introduced as the non-aromatic and non-chlorinated solvent for processing of polymer light-emitting diodes (PLEDs) and organic field effect transistors (OFETs). It was found that d-limonene could be a good solvent for a blue-emitting polyfluorene-based random copolymer for PLEDs and an alternating copolymer FBT-Th₄(1,4) with high hole mobility (μ_h) for OFETs. In comparisons to routine solvent-casted films of the two conjugated polymers, the resulting d-limonene-deposited films could show comparable film qualities, based on UV–vis absorption spectra and observations by atomic force microscopy (AFM). With d-limonene as the processing solvent, efficient blue PLEDs with CIE coordinates of (0.16, 0.16), maximum external quantum efficiency of 3.57%, and luminous efficiency of 3.66 cd/A, and OFETs with outstanding μ_h of 1.06 cm² (V s)⁻¹ were demonstrated. Our results suggest that d-limonene would be a promising non-aromatic and non-chlorinated solvent for solution processing of conjugated polymers and molecules for optoelectronic device applications.     

Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni²⁺ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg²⁺ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO₂ adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO₂ methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg²⁺-containing MOF framework, the composite system retains a portion of its CO₂ adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO₂ utilization.     

Atomistic insight into the hydration and proton conducting mechanisms of the cobalt doped Ruddlesden-Popper structure Sr3Fe2O7-δ

Sr₃Fe₂O_7-δ (SFO) with two-layer Ruddlesden-Popper (R–P) structure has recently been proved to be a promising material for the single phase cathode in proton conducting solid oxide fuel cells (P–SOFCs). To investigate the hydration reactions and proton conducting mechanisms of SFO and cobalt doped SFO (SFCO), both bulk and surface properties were calculated. We conclude that R–P structures have advantages in P–SOFCs. The unique Sr–O–M layer can facilitate the hydration process. Although in Sr–O–F and Sr–O–N layers, it is difficult for the formation and migration of oxygen vacancies, protons are most stable. Furthermore, cobalt doping can not only improve the electronic conductivity but also enhance surface properties of SFCO. The easily exposed Co–Fe–O surface can also facilitate the hydration reactions on the surface. Our work could give an informative insight into the relationships among the doped elements, the R–P structures, the hydration process and the proton conducting properties.     

Polymer electrolytes and interfaces in solid-state lithium metal batteries

The polymer electrolyte based solid-state lithium metal batteries are the promising candidate for the high-energy electrochemical energy storage with high safety and stability. Moreover, the intrinsic properties of polymer electrolytes and interface contact between electrolyte and electrodes have played critical roles for determining the comprehensive performances of solid-state lithium metal batteries. In this review, the development of polymer electrolytes with the design strategies by functional units adjustments are firstly discussed. Then the interfaces between polymer electrolyte and cathode/anode, including the interface issues, remedy strategies for stabilizing the interface contact and reducing resistances, and the in-situ polymerization method for enhancing the compatibilities and assembling the batteries with favorable performances, have been introduced. Lastly, the perspectives on developing polymer electrolytes by functional units adjustment, and improving interface contact and stability by effective strategies for solid-state lithium metal batteries have been provided.