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Transition metal carbides, such as molybdenum carbides, are promising substitutes for noble metals as low-cost, durable electrocatalysts. Under ambient conditions, however, these carbides are subject to oxidation due to their oxophilic nature. The partially oxidized surface may possess both oxygen-modulated metallic-like hydrogen adsorption sites and Brønsted-acidic hydroxyl sites. However, the impact of surface oxidation on electrochemical processes such as the hydrogen evolution reaction (HER) has rarely been studied. Here, we synthesized β-Mo2C catalysts and oxidized their surfaces electrochemically to varying extents to study the effects of surface oxidation on HER activity. The degree of surface oxidation was controlled by applying different potential windows to metal carbide catalysts. The samples with varying degrees of surface oxidation were tested for their HER activity. Experimental data indicate that the Tafel slope for the HER and double-layer capacitance were negatively affected by surface oxidation, particularly due to the loss of carbon and the formation of electrochemically less active surface oxides. The surface oxidation was studied experimentally by X-ray photoelectron spectroscopy and simulated using density functional theory (DFT), ab initio thermodynamics, and charge transfer estimates. Our DFT calculation results suggest that the model β-Mo2C (011) surface favors the adsorption of O* from water during the electrochemical oxidation, giving rise to the anodic current. Oxygen atoms preferentially interact with surface C sites, forming stable –C＝O species and oxycarbide-like surfaces. Highly oxidized surfaces become kinetically unstable and undergo a deeper, substitutional oxidation through –C＝O replacement by O*, forming a thermodynamically stable Mo(IV) surface oxide, where each Mo atom coordinates with up to six O atoms. The rate-limiting step switches from CO desorption, occuring within the potential window from 0.28 to 0.51 V, to water dissociation above 0.51 V. The computational results agree well with experimental observations, such as the onset potential (0.6 V) for rapid surface oxidation. This work helps to unravel the details of evolution of surface sites during an oxidation process of molybdenum carbides along with their effects on catalytic properties and lays the foundation for their practical use in various applications. [ABSTRACT FROM AUTHOR]

The description of the design, manufacturing technology, and test results of thin-film solid-state lithium-ion batteries with a nanocomposite negative electrode Si@O@Al is given herein. This electrochemical system features the hike on the charging curve plateau, which is interpreted as the change from I–V of the Ti-Si@O@Al contact. The latter is due to the change in the type of silicon conductivity during lithiation, as a result of which the ohmic metal-semiconductor contact proves to be biased in the reverse direction, and the charging current is maintained by minority charge carriers. It is shown that the current-conducting component Si@O@Al is formed by a solid solution a-Si(Al), which has a p-type conductivity. The change in the type of conductivity occurs as a result of silicon compensation through lithiation. It was found that Si@O@Al is nonlinear conductor, which can be considered as a percolation cluster formed by amorphous silicon nanoparticles and molecular clusters of silicon dioxide. The height of the Schottky barrier of the Ti|a-Si(Al) contact and the electron affinity of the a-Si(Al) solid solution were estimated. [ABSTRACT FROM AUTHOR]

Along with the soaring demands for all-solid-state thin-film lithium-ion batteries, the problem of their energy density rise becomes very acute. The solution to this problem can be found in development of 3D batteries. The present work deals with the development of a technology for a 3D solid-state lithium-ion battery (3D SSLIB) manufacturing by plasma-chemical etching and magnetron sputtering technique. The results on testing of experimental samples of 3D SSLIB are presented. It was found that submicron-scale steps appearing on the surface of a 3D structure formed on Si substrate by the Bosch process radically change the crystal structure of the upper functional layers. Such changes can lead to disruption of the layers' continuity, especially that of the down conductors. It is shown that surface polishing by liquid etching of the SiO2 layer and silicon reoxidation leads to surface smoothing, the replacement of the dendrite structure of functional layers by a block structure, and a significant improvement in the capacitive characteristics of the battery. [ABSTRACT FROM AUTHOR]

A structural model of LiPON solid electrolyte, containing elements that simulate drift conductivity, diffusion conductivity, and leakage current was proposed. The dependence of the impedance of the structural model on frequency was calculated, and the parameters of the model at which the theoretical curve best approximates the experimental Nyquist diagrams were determined. Based on these data, the ion diffusion coefficient and conductivity of LiPON were calculated, which are D1 = 1.5 × 10-11 cm²/s and σ = 1.9 × 10-6 S/cm, respectively. [ABSTRACT FROM AUTHOR]

The works of Prof. B. A. Perepelitsa from Kharkov Polytechnic Institute and his disciples to develop an applied methodology of multiparameter mappings in relation to the profiling and functioning of complex curvilinear objects and transmission mechanisms in mechanical engineering, mainly with examples of gears, are presented. The completed review is gratefully devoted to the 10th anniversary of Fiability & Durability Journal, which has repeatedly provided its platform to the authors to highlight this development of the wide Romanian, European and world scientific community. [ABSTRACT FROM AUTHOR]

The structural approach stated in this paper allows to simulate the different plane kinematic curves without their concrete analytic equations. The summarized unified mapping system for rack gearing is used. The examples of plane kinematic curves received by the structural method on computer are adduced. [ABSTRACT FROM AUTHOR]

Adsorbate vibrational excitations are an important fingerprint of molecule/surface interactions, affecting temperature contributions to the free energy and impacting reaction rate and equilibrium constants. Furthermore, vibrational spectra aid in identifying species and adsorption sites present in experimental studies. Despite their importance, knowledge of how adsorbate frequencies scale across materials is lacking. Here, by combining previously reported experimental data and our own density-functional theory calculations, we reveal linear correlations between vibrational frequencies of adsorbates on transition metal surfaces. Through effective-medium theory, linear muffin-tin orbital theory, and the d-band model, we rationalize the squares of the frequencies to be fundamentally linear in their scaling across transition metal surfaces. We identify the adsorbate-binding energy as a descriptor for certain molecular vibrations and rigorously relate errors in frequencies to errors in adsorption energies. We also discuss the impact of scaling on surface thermochemistry and adsorbate coverage. [ABSTRACT FROM AUTHOR]

The selective ring-opening of cellulose-derived furanic molecules is a promising pathway for the production of industrially relevant linear oxygenates, such as 1,6-hexanediol. 2,5-Dimethylfuran (DMF) is employed as a model compound in a combined experimental and computational investigation to provide insights into the metal-catalyzed ring-opening. Ring-opening to 2-hexanol and 2-hexanone and ring-saturation to 2,5-dimethyltetrahydrofuran (DMTHF) are identified as two main parallel pathways. DFT calculations and microkinetic modeling indicate that DMF adsorbs on Ru in an open-ring configuration, which is potentially a common surface intermediate that leads to both ring-opening and ring-saturation products. Although the activation barriers for the two pathways are comparable, the formation of DMTHF is more thermodynamically favorable. In addition, steric interactions with co-adsorbed 2-propoxyl, derived from the solvent, and the oxophilic nature of Ru play key roles to determine the product distribution: the former favors less bulky, that is, ring-closed, intermediates, and the latter retards O−H bond formation. Finally, we show that the hydrodeoxygenation of oxygenated furanics, such as 5-methylfurfural and (5-methyl-2-furyl)methanol, on Ru occurs preferentially at oxygen-containing side groups to form DMF, followed by either ring-opening or ring-saturation. [ABSTRACT FROM AUTHOR]

C-O bond activation on monofunctional catalysts (metals, carbides, and oxides) is challenging due to activity constraints imposed by energy scaling relationships. Yet, contrary to predictions, recently discovered multifunctional metal/metal oxide catalysts (e.g., Rh/ReOx, Rh/MoOx, Ir/VOx) demonstrate unusually high C-O scission activity at moderate temperatures. Herein, we use extensive density functional theory calculations, first-principles microkinetic modeling, and electronic structure analysis to elucidate the metal/metal oxide synergy in the Ru/RuO2 catalyst, which enables up to 76% yield of the C-O scission product (2-methyl furan) in catalytic transfer hydrogenolysis of furfural at low temperatures. Our key mechanistic finding is a facile radical-mediated C-O bond activation on RuO2 oxygen vacancies, which directly leads to a weakly bound final product. This is the first time the radical reduction mechanism is reported in heterogeneous catalysis at temperatures <200 °C. We attribute the unique catalytic properties to the formation of a conjugation-stabilized furfuryl radical upon C-O bond scission, the strong hydroxyl affinity of oxygen vacancies due to the metallic character of RuO2, and the acid-base heterogeneity of the oxide surface. The conjugation-driven radical-assisted C-O bond scission applies to any catalytic surface that preserves the π-electron system of the reactant and leads to C-O selectivity enhancement, with notable examples including Cu, H-covered Pd, self-assembled monolayers on Pd, and oxygen-covered Mo2C. Furthermore, we reveal the cooperativity of active sites in multifunctional catalysts. The mechanism is fully consistent with kinetic studies and isotopic labeling experiments, and the insights gained might prove useful more broadly in overcoming activity constraints induced by energy scaling relationships. [ABSTRACT FROM AUTHOR]

The questions of design research of noncylindrical tooth surfaces for two-parameter gearing on example of bevel gears with constant normal pitch forgearing variators are been considered. Engineering is based on the special applied development of the mathematical theory of multiparametric mappings of space. [ABSTRACT FROM AUTHOR]

We propose non-parametric methods for both local and global sensitivity analysis of chemical reaction models with correlated parameter dependencies. The developed mathematical and statistical tools are applied to a benchmark Langmuir competitive adsorption model on a close packed platinum surface, whose parameters, estimated from quantum-scale computations, are correlated and are limited in size (small data). The proposed mathematical methodology employs gradient-based methods to compute sensitivity indices. We observe that ranking influential parameters depends critically on whether or not correlations between parameters are taken into account. The impact of uncertainty in the correlation and the necessity of the proposed non-parametric perspective are demonstrated. [ABSTRACT FROM AUTHOR]

The article presents a study on electrochemical recycling of homogeneous catalysts. It discusses the Redox-mediated electrosorption for reversible catalyst recycling, electrode cycling, and mechanistic electrochemical studies of metal interaction. It outlines the scalability and favorable technoeconomics of electrochemical recycling.

The questions of tooling design for production of advanced gears are considered. Engineering is based on the special applied development of the mathematical theory of multiparametric mappings of space. In fulfilled engineering of gear cutting tools for shaping of noninvolute gears it is provided for exclusion of distorted profiling after tool regrinds. There are proposed calculation algorithms, which may be used in dataware of respective CAD/CAM systems of maintenance for tooling backup. Among developed tools there are assembled shaping cutters with prismatic and round cutters. Compensatory possibilities of proposed assembled shaping cutters are ensured by repositioning of shaped cutting edges after their regrindings: by linear displacement of prismatic shaped cutters and angular displacement of round ones respectively [ABSTRACT FROM AUTHOR]

In this article, the relevance of the study of gears with a complex non-involute profile of the tooth flanks is justified. For the subsequent study of non-involute gearings, the task of mathematical modeling of the profile of a gear-cutting rolling tool for machining of noninvolute gear wheels is solved. As a profile of the tooth flank of a rack, a certain section of one of the previously simulated flat kinematic curves is considered. Based on the algorithm for calculating the profile of envelope surfaces, a method for geometric analysis of the process of surfaces shaping by rolling gear cutting tools has been developed. Using computer graphics, the sequential shaping of the teeth space of non-involute gear wheels processed by rolling gear cutting tools with a given tooth profile was studied. [ABSTRACT FROM AUTHOR]

Data on content of 90Sr, 137Cs, 239,240Pu and 3H in water of the Tobol–Irtysh part of the Techa–Iset–Tobol–Irtysh–Ob river system (through which the “Mayak” PA radioactive wastes are transported) are presented and discussed. The data were received in 2004–2005 under the ISTC project on radioecological monitoring of the Tobol and Irtysh rivers. Monthly observations of 137Cs, 90Sr and 3H content in water in the area of the Tobol and Irtysh confluence have been conducted starting from May 2004. To obtain information on the investigated river system as a whole, the radioecological survey of the Tobol and Irtysh rivers at the section from the mouth of the Iset River to the confluence with the Ob River was carried out in 2004. It is shown that the impact of “Mayak” PA waste transport by 90Sr is distinctly traced as far as the area of the Irtysh and Ob confluence. [Copyright &y& Elsevier]

Leveraging specific noncovalent interactions can broaden the mechanims for selective electrochemical separations beyond solely electrostatic interactions. Here, we explore redox-responsive halogen bonding (XB) for selective electrosorption in nonaqueous media, by taking advantage of directional interactions of XB alongisde a cooperative and synergistic ferrocene redox-center. We designed and evaluated a new redox-active XB donor polymer, poly(5-iodo-4-ferrocenyl-1-(4-vinylbenzyl)-1 H -1,2,3-triazole) (P(FcTS-I)), for the electrochemically switchable binding and release of target organic and inorganic ions at a heterogeneous interface. Under applied potential, the oxidized ferrocene amplifies the halogen binding site, leading to significantly enhanced uptake and selectivity towards key inorganic and organic species, including chloride, bisulfate, and benzenesulfonate, compared to the open-circuit potential or the hydrogen bonding donor analog. Density functional theory calculations, as well as spectroscopic analysis, offer mechanistic insight into the degree of amplification of σ-holes at a molecular level, with selectivity modulated by charge transfer and dispersion interactions. Our work highlights the potential of XB in selective electrosorption by uniquely leveraging noncovalent interactions for redox-mediated electrochemical separations., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Photoelectrochemical (PEC) conversion is a promising way to use methane (CH 4 ) as a chemical building block without harsh conditions. However, the PEC conversion of CH 4 to value-added chemicals remains challenging due to the thermodynamically favorable overoxidation of CH 4 . Here, we report WO 3 nanotube (NT) photoelectrocatalysts for PEC CH 4 conversion with high liquid product selectivity through defect engineering. By tuning the flame reduction treatment, we carefully controlled the oxygen vacancies of WO 3 NTs. The optimally reduced WO 3 NTs suppressed overoxidation of CH 4 showing a high total C1 liquid selectivity of 69.4% and a production rate of 0.174 μmol cm -2 h -1 . Scanning electrochemical microscopy revealed that oxygen vacancies can restrain the production of hydroxyl radicals, which, in excess, could further oxidize C1 intermediates to CO 2 . Additionally, band diagram analysis and computational studies elucidated that oxygen vacancies thermodynamically suppress overoxidation. This work introduces a strategy for understanding and controlling the selectivity of photoelectrocatalysts for direct conversion of CH 4 to liquids.

It is widely accepted that energetics of chemical bond breaking and formation can be described with simple mathematical forms only at the expense of extensive parameterization. In this work, the discovery of a simple tight-binding-type mathematical framework that can accurately predict the relative energetics of regular H x polygons (2 ≤ x ≤ 15) in the ground states with their respective spin multiplicities using no parameters has been reported. The framework recasts Hückel theory in a density functional theory form by making use of Anderson and Adams-Gilbert theories of localized orbitals. For the systems examined, the method exhibits mean absolute errors of ∼0.02 Å (edge lengths) and ∼0.15 eV/atom (energy minima) relative to correlated-electron quantum chemistry calculations. Its accuracy is found to be comparable to the generalized gradient approximation and superior to standard parameterized tight binding and reactive potentials applied to H x structures. Generalization of the theoretical framework to systems of many-electron atoms is presented, along with the comparison of the method to existing semiempirical tight binding and bond order potential approaches.

Canonical descriptions of multistep biomolecular transformations generally follow a single-pathway viewpoint, with a series of transitions through intermediates converting reactants to products or repeating a conformational cycle. However, mounting evidence suggests that more complexity and pathway heterogeneity are mechanistically relevant due to the statistical distribution of multiple interconnected rate processes. Making sense of such pathway complexity remains a significant challenge. To better understand the role and relevance of pathway heterogeneity, we herein probe the chemical reaction network of a Cl - /H + antiporter, ClC-ec1, and analyze reaction pathways using multiscale kinetic modeling (MKM). This approach allows us to describe the nature of the competing pathways and how they change as a function of pH. We reveal that although pH-dependent Cl - /H + transport rates are largely regulated by the charge state of amino acid E148, the charge state of E203 determines relative contributions from coexisting pathways and can shift the flux pH-dependence. The selection of pathways via E203 explains how ionizable mutations (D/H/K/R) would impact the ClC-ec1 bioactivity from a kinetic perspective and lends further support to the indispensability of an internal glutamate in ClC antiporters. Our results demonstrate how quantifying the kinetic selection of competing pathways under varying conditions leads to a deeper understanding of the Cl - /H + exchange mechanism and can suggest new approaches for mechanistic control.

Colloidal tin oxide with an average particle size of 3.5 nm, which was ex-situ synthesized by the sol-gel method, has been attached to the surface of amino-functionalized poly(acrylate-co-silane) latex particles with a diameter of 100 nm to yield a composite with selective sorption properties toward Co(2+) ions. Electrokinetic properties and the colloidal stability of the synthesized latex/SnO2 composites have been evaluated in dependence on SnO2 content and pH; the sorption capacity and distribution coefficients of composites for Co(2+) ions were in accordance with the SnO2 content and its sorption performance as an individual compound. Composite coatings obtained by casting latex/SnO2 dispersions on quartz sand spiked with (57)Co radionuclide have efficiently eliminated radionuclides migration from the surface when the SnO2 volume fraction in the film was 3.5-4.7%. Furthermore, at these SnO2 loadings, the composite coatings retained the coherent structure of the original latex coating with SnO2 particles homogeneously distributed over the film thickness. The presence of competing Ca(2+) ions in the leaching media at a concentration of above 0.01 mol/L results in a decrease of the distribution coefficients of the latex/SnO2 composite and significantly higher (57)Co leaching. The value of the distribution coefficient of the sorption material to be used in latex composite coatings to prevent migration of radionuclides shall be close to 10(6) mL/g.