Search

The transformation of 2 ¯ 01 β - Ga 2 O 3 to h- GaN under exposure to RF nitrogen plasma was monitored in situ by reflection high-energy electron diffraction. Analysis of the reaction kinetics reveals that the nitridation process is initiated by the formation of an oxynitride phase and proceeds via two-dimensional nucleation and growth of wurtzite GaN grains. X-ray photoelectron spectra suggest a Ga − (N x O 1 − x) type configuration dominates the surface early in the nitridation process. The surface restructuring is followed by a diffusion-fed phase transformation, which propagates the wurzite GaN structure into the substrate upon reaching 70 % nitrogen anion site occupation, corresponding to the oxygen solubility in h - GaN. A direct correlation is observed between the nitridated film morphology and the epitaxial film crystallinity, demonstrating control of the residual strain, lateral coherence, and mosaicity in subsequent GaN epitaxy by the nitridation conditions. This study provides mechanistic details of the nitridation reaction of 2 ¯ 01 β - Ga 2 O 3 facilitating the optimization of the nitridation process toward improving GaN - 2 ¯ 01 β - Ga 2 O 3 heterojunctions. [ABSTRACT FROM AUTHOR]

We introduce a theoretical framework to study the kinetics of the chemical reactions involving transitions between electronic states with different spin quantum numbers in an external magnetic field. The new equations for calculating transition probabilities and rate constants are used to generalize the nonadiabatic statistical theory, which now accounts for both the spin–orbit and Zeeman couplings between electronic states. Focusing on the singlet–triplet transitions, we define two dimensionless parameters to characterize (1) the magnetic field strength relative to the strength of spin–orbit coupling and (2) the relative magnitudes of the spin–orbit coupling matrix elements that couple the singlet state to different components of the triplet state. Based on the values of these dimensionless parameters, we define distinct coupling regimes and propose specific approaches to calculating the transition probabilities and rate constants in these regimes. We apply the introduced theoretical framework to study the effect of an external magnetic field on the kinetics of spin-forbidden isomerization of the Ni(dpp)Cl2 [dpp = 1,3-bis(diphenylphosphino)propane] complex in the strong and weak field regimes. Our calculations predict that in a magnetic field of 50 T, the isomerization rate constant increases by about 10%. We hope this work will facilitate renewed efforts in controlling spin-dependent chemical reactions with an external magnetic field. [ABSTRACT FROM AUTHOR]

Transition state theory (TST) provides a framework to estimate the rate of chemical reactions. Despite its great success with many reaction systems, the underlying assumptions such as local equilibrium and nonrecrossing do not necessarily hold in all cases. Although dynamical systems theory can provide the mathematical foundation of reaction tubes existing in phase space that enables us to predict the fate of reactions free from the assumptions of TST, numerical demonstrations for large systems have been yet one of the challenges. Here, we propose a dimensionality reduction algorithm to demonstrate structures in phase space (called reactive islands) that predict reactivity in systems with many degrees of freedom. The core of this method is the application of supervised principal component analysis, where a coordinate transformation is performed to preserve the dynamical information on reactivity (i.e., to which potential basin the system moves from a region of interest) as much as possible. The reactive island structures are expected to be reflected in the transformed, low-dimensional phase space. As an illustrative example, the algorithm is scrutinized using a modified Hénon–Heiles Hamiltonian system extended to many degrees of freedom, which has three channels leading to three different products from one stable potential basin. It is shown that our algorithm can predict the reactivity in the transformed, low-dimensional coordinate system better than a naïve coordinate system and that the reactivity distribution in the transformed low-dimensional space is considered to reflect the underlying reactive islands. [ABSTRACT FROM AUTHOR]

Chemical reactions and vapor–liquid equilibria for molten lithium hydroxide (LiOH) were studied using molecular dynamics simulations and a deep potential (DP) model. The neural network for the model was trained on quantum density functional theory data for a range of conditions. The DP model allows simulations over timescales of hundreds of ns, which provide equilibrium compositions for the systems of interest. Single-phase NPT simulations of the liquid show the decomposition of LiOH into lithium oxide (Li2O) and dissolved water (H2O). These DP results were validated by direct ab initio molecular dynamics simulations that confirmed the accuracy of the model with respect to reaction kinetics and equilibrium properties of the melt. The reactive vapor–liquid behavior of this system was subsequently studied using direct coexistence interfacial DP simulations. Partial pressures of H2O in the vapor are found to be in close agreement with available experimental measurements. By fitting temperature-dependent expressions for the reaction equilibrium and Henry's law constants, the equilibrium composition for any given initial composition and temperature can be quantitatively modeled. For high initial concentrations of Li2O or H2O, mixtures of LiOH + Li2O/H2O are found to undergo phase separation. The present study illustrates how DP-based molecular dynamics simulations can be used for quantitative modeling of multiphase reactive behavior with the accuracy of the underlying ab initio quantum chemical methods. [ABSTRACT FROM AUTHOR]

Lithium–sulfur batteries hold great promise as energy storage systems, but the shuttle effect of lithium polysulfides (LiPS) and large volume variation limit their capacity and cycle life. We have developed CoFe alloy wrapped in N-doped porous carbon spheres (e-CF@NC) with a core–shell structure through simple copolymerization and pyrolysis. The nitrogen-doped porous carbon shell provides electron and ion transport channels and more active sites for electrolyte ion adsorption. The high chemically stable carbon can limit the segregation of polysulfides, further improving the battery cycling stability. Besides, the inside CoFe alloy particles catalyze the conversion between LiPS and Li2S, speeding up reaction kinetics and reducing solvation of active sites. Consequently, lithium–sulfur batteries with e-CF@NC-2 as the cathode display a high initial specific capacity of 1146 mA h g−1 at 0.1 C, excellent rate performance (891 mA h g−1 at 1 C, 741 mA h g−1 at 2 C), and satisfied cycle stability (average capacity decay rate of 0.033% per cycle at 1 C for 300 cycles), demonstrating significant application potential. [ABSTRACT FROM AUTHOR]

Sum frequency generation vibrational spectroscopy (SFG) was applied to characterize the interfacial adhesion chemistry at several buried polymer interfaces in both model systems and blown multilayer films. Anhydride/acid modified polyolefins are used as tie layers to bond dissimilar polymers in multilayer barrier structures. In these films, the interfacial reactions between the barrier polymers, such as ethylene vinyl alcohol (EVOH) or nylon, and the grafted anhydrides/acids provide covalent linkages that enhance adhesion. However, the bonding strengths vary for different polymer–tie layer combinations. Here, using SFG, we aim to provide a systematic study on four common polymer–tie interfaces, including EVOH/polypropylene–tie, EVOH/polyethylene–tie, nylon/polypropylene–tie, and nylon/polyethylene–tie, to understand how the adhesion chemistry varies and its impact on the measured adhesion. Our SFG studies suggest that adhesion enhancement is driven by a combination of reaction kinetics and the interfacial enrichment of the anhydride/acid, resulting in stronger adhesion in the case of nylon. This observation matches well with the higher adhesion observed in the nylon/tie systems in both lap shear and peel test measurements. In addition, in the polypropylene–tie systems, grafted oligomers due to chain scission may migrate to the interface, affecting the adhesion. These by-products can react or interfere with the barrier–tie chemistry, resulting in reduced adhesion strength in the polypropylene–tie system. [ABSTRACT FROM AUTHOR]

Only copper-related deep-level centers are produced by room-temperature MeV-electron irradiation in silicon doped with a high concentration of mobile interstitial copper atoms. In oxygen-lean FZ-Si, the well-known Cu PL centers of four copper atoms show up in the DLTS, Laplace-DLTS, and photoluminescence measurements. In oxygen-rich Cz-Si, two new centers appear due to the irradiation at the expense of the Cu PL defect. Reaction kinetics analysis correlates the new defects with oxygen, copper, and the irradiation-induced vacancy. The new defects are annealed at temperatures of 150–250 ° C and, after passing through two more new configurations, are transformed into Cu PL . The strong similarities to Cu PL suggest that all four new defects are Cu PL -like complexes of four copper atoms perturbed by a nearby oxygen. [ABSTRACT FROM AUTHOR]

Meso-scale calculations of energy localization and initiation in energetic material microstructures must capture the deformation and collapse of pores and high-temperature shear bands, which lead to hotspots. Because chemical reaction rates depend sensitively on temperature, predictive continuum models need to get the pore-collapse dynamics and resulting hotspot temperatures right; this imposes stringent demands on the fidelity of thermophysical model forms and parameters and on the numerical methods employed to perform high-resolution meso-scale calculations. Here, continuum material models for β-HMX are examined in the context of shock-induced pore collapse, treating predictions from all-atom molecular dynamics (MD) simulations as ground truth. Using atomistics-consistent material properties, we show that the currently available strength models for HMX fail to correctly capture pore collapse and hotspot temperatures. Insights from MD are then employed to advance a Modified Johnson–Cook (M-JC) strength model, which is shown to capture key aspects of the physics of shock-induced localization in HMX. The study culminates in a MD-guided strength model for β-HMX that produces continuum pore-collapse results in better alignment on several aspects with those predicted by MD, including pore-collapse mechanism and rate, shear-band formation in the collapse zone, and temperature, strain, and stress fields in the hotspot zone and the surrounding material. The resulting MD-informed/MD-determined M-JC model should improve the fidelity of meso-scale simulations to predict the detonation initiation of HMX-based energetic materials in microstructure-aware multi-scale frameworks. [ABSTRACT FROM AUTHOR]

We present the development of a new astrochemical research tool, HILTRAC, the Highly Instrumented Low Temperature ReAction Chamber. The instrument is based on a pulsed form of the CRESU (Cinétique de Réaction en Écoulement Supersonique Uniforme, meaning reaction kinetics in a uniform supersonic flow) apparatus, with the aim of collecting kinetics and spectroscopic information on gas phase chemical reactions important in interstellar space or planetary atmospheres. We discuss the apparatus design and its flexibility, the implementation of pulsed laser photolysis followed by laser induced fluorescence, and the first implementation of direct infrared frequency comb spectroscopy (DFCS) coupled to the uniform supersonic flow. Achievable flow temperatures range from 32(3) to 111(9) K, characterizing a total of five Laval nozzles for use with N2 and Ar buffer gases by impact pressure measurements. These results were further validated using LIF and direct frequency comb spectroscopy measurements of the CH radical and OCS, respectively. Spectroscopic constants and linelists for OCS are reported for the 1001 band near 2890–2940 cm−1 for both OC32S and OC34S, measured using DFCS. Additional peaks in the spectrum are tentatively assigned to the OCS-Ar complex. The first reaction rate coefficients for the CH + OCS reaction measured between 32(3) and 58(5) K are reported. The reaction rate coefficient at 32(3) K was measured to be 3.9(4) × 10−10 cm3 molecule−1 s−1 and the reaction was found to exhibit no observable temperature dependence over this low temperature range. [ABSTRACT FROM AUTHOR]

Transition-metal selenides have been extensively studied as promising electrode materials for supercapacitors. Engineering amorphous/crystalline heterostructures is an effective strategy to improve rich active sites for accelerating redox reaction kinetics but still lacks exploration. In this study, an amorphous/crystalline heterostructure was designed and constructed by selenizing the self-sacrificial template NiMnS to generate amorphous Mn/polycrystalline Ni0.85Se–NiSe2 heterophase via the phase transformation from metal sulfide into metal selenide. The synergy of the complementary multi-components and amorphous/polycrystalline heterophase could enrich electron/ion-transport channels and expose abundant active sites, which accelerated electron/ion transfer and Faradaic reaction kinetics during charging/discharging. As expected, the optimal NiMnSe exhibited a high specific charge (1389.1 C g−1 at 1 A g−1), a good rate capability, and an excellent lifespan (88.9% retention). Moreover, the fabricated NiMnSe//activated carbon device achieved a long cycle life and energy density of 48.0 W h kg−1 at 800 W kg−1, shedding light on the potential for use in practical applications, such as electrochemical energy-storage devices. [ABSTRACT FROM AUTHOR]

The committor constitutes the primary quantity of interest within chemical kinetics as it is understood to encode the ideal reaction coordinate for a rare reactive event. We show the generative utility of the committor in that it can be used explicitly to produce a reactive trajectory ensemble that exhibits numerically exact statistics as that of the original transition path ensemble. This is done by relating a time-dependent analog of the committor that solves a generalized bridge problem to the splitting probability that solves a boundary value problem under a bistable assumption. By invoking stochastic optimal control and spectral theory, we derive a general form for the optimal controller of a bridge process that connects two metastable states expressed in terms of the splitting probability. This formalism offers an alternative perspective into the role of the committor and its gradients in that they encode force fields that guarantee reactivity, generating trajectories that are statistically identical to the way that a system would react autonomously. [ABSTRACT FROM AUTHOR]

The development and technological applications of molecular spin systems require versatile experimental techniques to characterize and control their static and dynamic magnetic properties. In the latter case, bulk spectroscopic and magnetometric techniques, such as AC magnetometry and pulsed electron paramagnetic resonance, are usually employed, showing high sensitivity, wide dynamic range, and flexibility. They are based on creating a nonequilibrium state either by changing the magnetic field or by applying resonant microwave radiation. Another possible source of perturbation is a laser pulse that rapidly heats the sample. This approach has proven to be one of the most useful techniques for studying the kinetics and mechanism of chemical and biochemical reactions. Inspired by these works, we propose an inductive detection of temperature-induced magnetization dynamics as applied to the study of molecular spin systems and describe the general design and construction of a particular induction probehead, taking into account the constraints imposed by the cryostat and electromagnet. To evaluate the performance, several coordination compounds of VO2+, Co2+, and Dy3+ were investigated using low-energy pulses of a terahertz free electron laser of the Novosibirsk free electron laser facility as a heat source. All measured magnetization dynamics were qualitatively or quantitatively described using a proposed basic theoretical model and compared with the data obtained by alternating current magnetometry. Based on the results of the research, the possible scope of applications of inductive detection and its advantages and disadvantages in comparison with standard methods are discussed. [ABSTRACT FROM AUTHOR]

We demonstrate and characterize a first-principles approach to modeling the mass action dynamics of metabolism. Starting from a basic definition of entropy expressed as a multinomial probability density using Boltzmann probabilities with standard chemical potentials, we derive and compare the free energy dissipation and the entropy production rates. We express the relation between entropy production and the chemical master equation for modeling metabolism, which unifies chemical kinetics and chemical thermodynamics. Because prediction uncertainty with respect to parameter variability is frequently a concern with mass action models utilizing rate constants, we compare and contrast the maximum entropy model, which has its own set of rate parameters, to a population of standard mass action models in which the rate constants are randomly chosen. We show that a maximum entropy model is characterized by a high probability of free energy dissipation rate and likewise entropy production rate, relative to other models. We then characterize the variability of the maximum entropy model predictions with respect to uncertainties in parameters (standard free energies of formation) and with respect to ionic strengths typically found in a cell. [ABSTRACT FROM AUTHOR]

Utilizing thermochemical reactions for thermal energy storage and solar fuel production has been an emerging research topic. Thermal transport properties of the materials are an important parameter that can determine the kinetics and efficiency of thermochemical reactions. With the increasing number of new thermochemical materials (TCMs); however, there is a lack of reliable techniques to monitor the thermal transport property of the materials and their changes as a function of reactions in real time. In this work, we report the in situ monitoring of thermochemical reactions using modulated photothermal radiometry (MPR). The thermal conductivities of two TCMs, namely, calcium hydroxide (Ca(OH)2) and Ba0.15Sr0.85FeO3−δ (BSF1585), were measured as a function of temperature and time using the MPR technique. The measured thermal conductivities were correlated to the reaction. The work has two significant contributions to the research communities. First, it provides a non-invasive diagnostic tool for monitoring the thermal transport properties of TCMs that can potentially be a high-throughput measurement technique conducive to optimizing TCMs, reactors, and related thermal systems. Second, for TCMs that show observable changes in thermal transport properties, a correlation between the measured thermal conductivity and the conversion fraction of the reaction can be established for monitoring the reaction kinetics based on thermal characterization. [ABSTRACT FROM AUTHOR]

Experimental studies of the products of elementary gas-phase chemical reactions occurring at low temperatures (<50 K) are very scarce, but of importance for fundamental studies of reaction dynamics, comparisons with high-level quantum dynamical calculations, and, in particular, for providing data for the modeling of cold astrophysical environments, such as dense interstellar clouds, the atmospheres of the outer planets, and cometary comae. This study describes the construction and testing of a new apparatus designed to measure product branching fractions of elementary bimolecular gas-phase reactions at low temperatures. It combines chirped-pulse Fourier transform millimeter wave spectroscopy with continuous uniform supersonic flows and high repetition rate laser photolysis. After a comprehensive description of the apparatus, the experimental procedures and data processing protocols used for signal recovery, the capabilities of the instrument are explored by the study of the photodissociation of acrylonitrile and the detection of two of its photoproducts, HC3N and HCN. A description is then given of a study of the reactions of the CN radical with C2H2 at 30 K, detecting the HC3N product, and with C2H6 at 10 K, detecting the HCN product. A calibration of these two products is finally attempted using the photodissociation of acrylonitrile as a reference process. The limitations and possible improvements in the instrument are discussed in conclusion. [ABSTRACT FROM AUTHOR]

The atmospheric reactions are mainly initiated by hydroxyl radical (OH). Here, we choose the C2H4 + OH reaction as a model reaction for other reactions of OH with alkenes. We use the GMM(P).L//CCSD(T)-F12a/cc-pVTZ-F12 theoretical method as the benchmark results close to the approximation of CCSDTQ(P)/CBS accuracy to investigate the C2H4 + OH reaction. The rate constants for the C2H4 + OH reaction at high-pressure limit were calculated by using the dual-level strategy. It integrates the transition state theory rate constant calculated by GMM(P).L//CCSD(T)-F12a/cc-pVTZ-F12 with the canonical variational transition state theory containing small-curvature tunneling (CVT/SCT) calculated by using the M11-L functional method with the MG3S basis set. The rate constants of C2H4 + OH at different pressures were obtained by using both the system-specific quantum Rice–Ramsperger–Kassel (SS-QRRK) theory and master equation method. The calculated results uncover that both the calculated rate constants at different pressures and temperatures are quantitatively consistent with the values obtained by the experimental measurements in the C2H4 + OH reaction. We find that the post-CCSD(T) contributions to the barrier height for the C2H4 + OH reaction are significant with the calculated value of −0.38 kcal/mol. We also find that the rate determining step is only dominated by the tight transition state under atmospheric conditions, whereas previous investigations indicated that the rate constants were controlled by both the loose and tight transition states in the C2H4 + OH reaction. The present findings unravel that it is an important factor for the effect of torsional anharmonicity on quantitative kinetics. [ABSTRACT FROM AUTHOR]

The influence of microstructure on the response of energetic structural materials (ESMs) under shock conditions remains inadequately quantified, and the energy release process is not thoroughly understood. In this work, taking the classical Ni/Al ESM as an example, the shock response was investigated by the shock compression theory with the microstructure-based chemical reaction kinetics model. This theory mainly refers to the equation of the state of multi-component materials with mixture rule, and the reaction at the particle contact interface is built to form the multiscale thermodynamics model. The physical states of material after shock, including relative volume, temperature, and extent of reaction, were analyzed. The results revealed the effect of the burn velocity, particle size and molar ratio on the shock response. Furthermore, the model facilitates a comprehensive understanding of energy release, the extent of the intermetallic reaction, and the oxidation reaction. Despite the involvement of only a small portion of materials in the oxidation reaction, the energy release proportion was comparable to that of the intermetallic reaction. Additionally, insights into the effect of the microstructure on the energy release revealed by the model matched the tests well. [ABSTRACT FROM AUTHOR]

The rates and pathways of chemical reactions at metal surfaces can be strongly influenced by energy dissipation due to the nonadiabatic excitation of metallic conduction electrons. The introduction of frictional forces to account for this dissipation has been quite successful in situations for which the nonadiabatic coupling is weak. However, in cases where nonadiabatic coupling is strong, such as when electron transfer occurs, the friction model is likely to break down. Ryabinkin and Izmaylov have proposed 2-state and 3-state alternatives to the friction model for introducing electronic dissipation in molecular dynamics simulations. Here, we examine their 2-state model using some simple examples of atom–surface scattering. We find that, with the addition of decoherence, the 2-state model can produce quite promising results. [ABSTRACT FROM AUTHOR]

We present a theory of the effect of quantum tunneling on the basic parameter that characterizes the effect of pressure on the rate constant of chemical reactions in a dense phase, the activation volume. This theory results in combining, on the one hand, the extreme pressure polarizable continuum model, a quantum chemical method to describe the effect of pressure on the reaction energy profile in a dense medium, and, on the other hand, the semiclassical version of the transition state theory, which includes the effect of quantum tunneling through a transmission coefficient. The theory has been applied to the study of the activation volume of the model reaction of hydrogen transfer between methyl radical and methane, including the primary isotope substitution of hydrogen with deuterium (H/D). The analysis of the numerical results offers, for the first time, a clear insight into the effect of quantum tunneling on the activation volume for this hydrogen transfer reaction: this effect results from the different influences that pressure has on the competing thermal and tunneling reaction mechanisms. Furthermore, the computed kinetic isotope effect (H/D) on the activation volume for this model hydrogen transfer correlates well with the experimental data for more complex hydrogen transfer reactions. [ABSTRACT FROM AUTHOR]

The reactivity of heterogeneous energetic materials (HEMs) intimately depends on the underlying microstructural effects. For reactive materials, key factors include the microstructure distribution, morphology, size scale of heterogeneities, reactant mixing, and chemical kinetics of the reactants. We report the development of a mesoscale model for simulating the evolutions of the hotspot field and associated reaction processes when such materials are exposed to external excitations. The model explicitly accounts for microstructure, interdiffusion between the reactant species, advection of the species mixture, and chemical kinetics of the reaction. An Arrhenius relation is used to capture the rate of reactive heat release. The particular material analyzed is a composite of poly(vinylidene fluoride-co-trifluoroethylene) and nanoaluminum [or P(VDF-TrFE)/nAl]. The excitation leading to the initial microstructural temperature increase that kicks off the exothermic reactive processes is the dissipative heating arising from dielectric breakdown under the electric field developed through piezoelectricity and flexoelectricity of P(VDF-TrFE). As such, the model resolves both the breakdown process and the diffusion, advection, and exothermic reaction processes. The evolutions of the temperature and species distribution fields under the combined effects of breakdown and chemistry are used to predict the effects of microstructure, diffusion, and kinetics on several key metrics characterizing the reactive responses of the material. This mesoscale framework admits the quantification of uncertainties in these predicted macroscopic behavior measures due to microstructure heterogeneity fluctuations through the use of multiple, random but statistically equivalent microstructure instantiations. Although the particular hotspot inducing mechanism considered is dielectric breakdown here, the framework can be adapted to analyze reaction initiation and propagation and establish microstructure–reaction behavior relations under other types of hotspot inducing mechanisms, such as thermomechanical inelastic dissipation, frictional heating, and laser or microwave excitation. [ABSTRACT FROM AUTHOR]

Interfacial enhancements of chemical reaction equilibria and rates in liquid droplets are predicted using a combined theoretical and experimental analysis strategy. Self-consistent solutions of reaction and adsorption equilibria indicate that interfacial reactivity enhancement is driven primarily by the adsorption free energy of the product (or activated complex). Reactant surface activity has a smaller indirect influence on reactivity due to compensating reactant interfacial concentration and adsorption free energy changes, as well as adsorption-induced depletion of the droplet core. Experimental air-water interfacial adsorption free energies and critical micelle concentration correlations provide quantitative surface activity estimates as a function of molecular structure, predicting an increase in interfacial reactivity with increasing product size and decreasing product polarity, aromaticity, and charge (but less so for anions than cations). Reactions with small, neutral, or charged products are predicted to have little reactivity enhancement at an air–water interface unless the product is rendered sufficiently surface active by, for example, interactions with interfacial water dangling OH groups, charge transfer, or voltage fluctuations. [ABSTRACT FROM AUTHOR]

The study and modeling of water exchange in complex media using different applications of diffusion and relaxation magnetic resonance (MR) have been of interest in recent years. Most models attempt to describe this process using a first order kinetics expression, which is appropriate to describe chemical exchange; however, it may not be suitable to describe diffusion-driven exchange since it has no direct relationship to diffusion dynamics of water molecules. In this paper, these limitations are addressed through a more general exchange expression that does consider such important properties. This exchange fraction expression features a multi-exponential recovery at short times and a mono-exponential decay at long times, both of which are not captured by the first order kinetics expression. Furthermore, simplified exchange expressions containing partial information of the analyzed system's diffusion and relaxation processes and geometry are proposed, which can potentially be employed in already established estimation protocols. Finally, exchange fractions estimated from simulated MR data and derived here were compared, showing qualitative similarities but quantitative differences, suggesting that the features of the derived exchange fraction in this paper can be partially recovered by employing an existing estimation framework. [ABSTRACT FROM AUTHOR]

Multi-scale predictive models for the shock sensitivity of energetic materials connect energy localization ("hotspots") in the microstructure to macro-scale detonation phenomena. Calculations of hotspot ignition and growth rely on models for chemical reaction rates expressed in Arrhenius forms; these chemical kinetic models, therefore, are foundational to the construction of physics-based, simulation-derived meso-informed closure (reactive burn) models. However, even for commonly used energetic materials (e.g., HMX in this paper) there are a wide variety of reaction rate models available. These available reaction rate models produce reaction time scales that vary by several orders of magnitude. From a multi-scale modeling standpoint, it is important to determine which model best represents the reactive response of the material. In this paper, we examine three global Arrhenius-form rate models that span the range of reaction time scales, namely, the Tarver 3-equation, the Henson 1-equation, and the Menikoff 1-equation models. They are employed in a meso-informed ignition and growth model which allows for connecting meso-scale hotspot dynamics to macro-scale shock-to-detonation transition. The ability of the three reaction models to reproduce experimentally observed sensitivity is assessed by comparing the predicted criticality envelope (Walker–Wasley curve) with experimental data for pressed HMX Class V microstructures. The results provide a guideline for model developers on the plausible range of time-to-ignition that are produced by physically correct Arrhenius rate models for HMX. [ABSTRACT FROM AUTHOR]

To cope with the shuttling of soluble lithium polysulfides in lithium–sulfur batteries, confinement tactics, such as trapping of sulfur within porous carbon structures, have been extensively studied. Although performance has improved a bit, the slow polysulfide conversion inducing fast capacity decay remains a big challenge. Herein, a NiS2/carbon (NiS2/C) composite with NiS2 nanoparticles embedded in a thin layer of carbon over the surface of micro-sized hollow structures has been prepared from Ni-metal–organic frameworks. These unique structures can physically entrap sulfur species and also influence their redox conversion kinetics. By improving the reaction kinetics of polysulfides, the NiS2/carbon@sulfur (NiS2/C@S) composite cathode with a suppressed shuttle effect shows a high columbic efficiency and decent rate performance. An initial capacity of 900 mAh g−1 at the rate of 1 C (1 C = 1675 mA g−1) and a low-capacity decline rate of 0.132% per cycle after 500 cycles are obtained, suggesting that this work provides a rational design of a sulfur cathode. [ABSTRACT FROM AUTHOR]

For photosensitive polyurethane systems, reactive diluents are indispensable components whose main role is to reduce the viscosity of the polyurethane prepolymer to meet the requirements of the photocurable 3D printing technology for high fluidity of the precursor solution. Generally, the reactive diluent would be involved in the photocuring reaction, which in turn has a remarkable impact on the mechanical, reaction kinetics, and thermodynamic characteristics of the photosensitive polyurethane system. However, this feature is usually neglected in the study of photosensitive urethane acrylate (PUA) systems, so there is a considerable necessity to investigate the mechanism of active diluents in the photocured reaction of PUA systems. In this work, the effects of α-methyl groups along the chains of diluent molecules on the photoreaction kinetics, photocurable 3D printing, mechanical and mechanical properties, and thermodynamic characteristics of PUAs were investigated employing hydroxyethyl methacrylate and hydroxyethyl acrylate as active diluents, respectively. The relationship between chemical structure and kinetics of PUA systems was also elucidated by using dynamic mechanical analysis tests. The results demonstrated that the α-methyl group blocks the migration of reactive radicals, reduces the efficiency of the photoreaction, and causes an increase in the rigidity and strength of the molecular chain. This study not only revealed the effect of α-methyl on the kinetic mechanical and thermal performance of PUA systems but also paves the way for the development of a new class of photosensitive PUA materials used for the photocurable 3D printing technology. [ABSTRACT FROM AUTHOR]

Photocatalytic water splitting for green hydrogen production is hindered by the sluggish kinetics of oxygen evolution reaction (OER). Loading a co-catalyst is essential for accelerating the kinetics, but the detailed reaction mechanism and role of the co-catalyst are still obscure. Here, we focus on cobalt oxide (CoOx) loaded on bismuth vanadate (BiVO4) to investigate the impact of CoOx on the OER mechanism. We employ photoelectrochemical impedance spectroscopy and simultaneous measurements of photoinduced absorption and photocurrent. The reduction of V5+ in BiVO4 promotes the formation of a surface state on CoOx that plays a crucial role in the OER. The third-order reaction rate with respect to photohole charge density indicates that reaction intermediate species accumulate in the surface state through a three-electron oxidation process prior to the rate-determining step. Increasing the excitation light intensity onto the CoOx-loaded anode improves the photoconversion efficiency significantly, suggesting that the OER reaction at dual sites in an amorphous CoOx(OH)y layer dominates over single sites. Therefore, CoOx is directly involved in the OER by providing effective reaction sites, stabilizing reaction intermediates, and improving the charge transfer rate. These insights help advance our understanding of co-catalyst-assisted OER to achieve efficient water splitting. [ABSTRACT FROM AUTHOR]

Chirped-Pulse Fourier-Transform millimeter wave (CP-FTmmW) spectroscopy is a powerful method that enables detection of quantum state specific reactants and products in mixtures. We have successfully coupled this technique with a pulsed uniform Laval flow system to study photodissociation and reactions at low temperature, which we refer to as CPUF ("Chirped-Pulse/Uniform flow"). Detection by CPUF requires monitoring the free induction decay (FID) of the rotational coherence. However, the high collision frequency in high-density uniform supersonic flows can interfere with the FID and attenuate the signal. One way to overcome this is to sample the flow, but this can cause interference from shocks in the sampling region. This led us to develop an extended Laval nozzle that creates a uniform flow within the nozzle itself, after which the gas undergoes a shock-free secondary expansion to cold, low pressure conditions ideal for CP-FTmmW detection. Impact pressure measurements, commonly used to characterize Laval flows, cannot be used to monitor the flow within the nozzle. Therefore, we implemented a REMPI (resonance-enhanced multiphoton ionization) detection scheme that allows the interrogation of the conditions of the flow directly inside the extended nozzle, confirming the fluid dynamics simulations of the flow environment. We describe the development of the new 20 K extended flow, along with its characterization using REMPI and computational fluid dynamics. Finally, we demonstrate its application to the first low temperature measurement of the reaction kinetics of HCO with O2 and obtain a rate coefficient at 20 K of 6.66 ± 0.47 × 10−11 cm3 molec−1 s−1. [ABSTRACT FROM AUTHOR]

The aim of this study is to suggest a novel approach for estimating the intramolecular mobility of a charge carrier that migrates within a polymer chain and is involved in a pair reaction with a particle located on the same chain. The approach is based on the effect of an external electric field on the migration rate and, consequently, the kinetics of the reaction. As a first step, this problem is considered a stochastic one-step process with absorbing and reflecting boundaries, and an analytical solution is obtained in the case that the second reactant is immobile. With the use of computer simulations of stochastic migration, the effect of the mobility of both reactants and the influence of the Coulomb interaction between them are considered. It is found that the ratio of the pair reaction rates with and without an external field is relatively little dependent on these factors and that the analytical expressions derived can be applied to estimate the relative mobility of recombining particles with accuracy better than a factor of two in many realistic situations. [ABSTRACT FROM AUTHOR]

Absolute line strengths of several transitions in the ν1 fundamental band of the hydroxyl radical (OH) have been measured by simultaneous determination of hydrogen peroxide (H2O2) and OH upon laser photolysis of H2O2. Based on the well-known quantum yield for the generation of OH radicals in the 248-nm photolysis of H2O2, the line strength of the OH radicals can be accurately derived by adopting the line strength of the well-characterized transitions of H2O2 and analyzing the difference absorbance time traces of H2O2 and OH obtained upon laser photolysis. Employing a synchronized two-color dual-comb spectrometer, we measured high-resolution time-resolved absorption spectra of H2O2 near 7.9 µm and the OH radical near 2.9 µm, simultaneously, under varied conditions. In addition to the studies of the line strengths of the selected H2O2 and OH transitions, the kinetics of the reaction between OH and H2O2 were investigated. A pressure-independent rate coefficient kOH+H2O2 was determined to be [1.97 (+0.10/−0.15)] × 10−12 cm3 molecule−1 s−1 at 296 K and compared with other experimental results. By carefully analyzing both high-resolution spectra and temporal absorbance profiles of H2O2 and OH, the uncertainty of the obtained OH line strengths can be achieved down to <10% in this work. Moreover, the proposed two-color time-resolved dual-comb spectroscopy provides a new approach for directly determining the line strengths of transient free radicals and holds promise for investigations on their self-reaction kinetics as well as radical–radical reactions. [ABSTRACT FROM AUTHOR]

Stochastic chemical kinetics is a widely used formalism for studying stochasticity of chemical reactions inside single cells. Experimental studies of reaction networks are generally performed with cells that are part of a growing population, yet the population context is rarely taken into account when models are developed. Models that neglect the population context lose their validity whenever the studied system influences traits of cells that can be selected in the population, a property that naturally arises in the complex interplay between single-cell and population dynamics of cell fate decision systems. Here, we represent such systems as absorbing continuous-time Markov chains. We show that conditioning on non-absorption allows one to derive a modified master equation that tracks the time evolution of the expected population composition within a growing population. This allows us to derive consistent population dynamics models from a specification of the single-cell process. We use this approach to classify cell fate decision systems into two types that lead to different characteristic phases in emerging population dynamics. Subsequently, we deploy the gained insights to experimentally study a recurrent problem in biology: how to link plasmid copy number fluctuations and plasmid loss events inside single cells to growth of cell populations in dynamically changing environments. [ABSTRACT FROM AUTHOR]

Kinetics of force-mediated chemical reactions of end-tethered polymers with varying chain length N in varying shear rate flow γ ̇ are explored via coarse-grained Brownian dynamics simulations. At fixed γ ̇ , force F along a polymer increases linearly with N as previously predicted; however, contrary to existing theory, the F(N) slope increases for N above a transition length that exhibits minimal dependence on γ ̇ . Force profiles are used in a stochastic model of a force-mediated reaction to compute the time for x percent of a polymer population to experience a reaction, tx. Observations are insensitive to the selected value of x in that tx data for varying N and γ ̇ can be consistently collapsed onto a single curve via appropriate scaling, with one master curve for systems below the transition N (small N) and another for those above (large N). Different force scaling for small and large N results in orders of magnitude difference in force-mediated reaction kinetics as represented by the population response time. Data presented illustrate the possibility of designing mechano-reactive polymer populations with highly controlled response to flow across a range in γ ̇ . [ABSTRACT FROM AUTHOR]

Calcium–alumino–silicate–hydrate (CaO–Al2O3–SiO2–H2O, or C–A–S–H) gel, which is the binding phase of cement-based materials, greatly influences concrete mechanical properties and durability. However, the atomic-scale kinetics of the aluminosilicate network condensation remains puzzling. Here, based on reactive molecular dynamics simulations of C–A–S–H systems formation with varying Al/Ca molar ratios, we study the kinetic mechanism of the hydrated aluminosilicate gels upon precipitation. We show that the condensation activation energy decreases with the Al/Ca molar ratio, which suggests that the concentration of the Al polytopes has a great effect on controlling the kinetics of the gelation reaction. Significantly, we demonstrate that 5-fold Al atoms are mainly forming at high Al/Ca molar ratios since there are insufficient hydrogen cations or extra calcium cations to compensate the negatively charged Al polytopes at high Al/Ca molar ratios during accelerated aging. [ABSTRACT FROM AUTHOR]

The computational modeling of electrochemical interfaces and their applications in electrocatalysis has attracted great attention in recent years. While tremendous progress has been made in this area, however, the accurate atomistic descriptions at the electrode/electrolyte interfaces remain a great challenge. The Computational Hydrogen Electrode (CHE) method and continuum modeling of the solvent and electrolyte interactions form the basis for most of these methodological developments. Several posterior corrections have been added to the CHE method to improve its accuracy and widen its applications. The most recently developed grand canonical potential approaches with the embedded diffuse layer models have shown considerable improvement in defining interfacial interactions at electrode/electrolyte interfaces over the state-of-the-art computational models for electrocatalysis. In this Review, we present an overview of these different computational models developed over the years to quantitatively probe the thermodynamics and kinetics of electrochemical reactions in the presence of an electrified catalyst surface under various electrochemical environments. We begin our discussion by giving a brief picture of the different continuum solvation approaches, implemented within the ab initio method to effectively model the solvent and electrolyte interactions. Next, we present the thermodynamic and kinetic modeling approaches to determine the activity and stability of the electrocatalysts. A few applications to these approaches are also discussed. We conclude by giving an outlook on the different machine learning models that have been integrated with the thermodynamic approaches to improve their efficiency and widen their applicability. [ABSTRACT FROM AUTHOR]

The behavior of energetic materials is significantly influenced by the spatial distributions of microstructure heterogeneities and voids. We pursue the concept of Functionally Graded Energetic Materials whose microstructure features (e.g., grain size, grain volume fraction, void size, and void volume fraction) change spatially such that they may allow the behavior of the materials to be tailored. We explore using gradients in the density of voids to alter the detonation behavior of a polymer-bonded explosive (PBX) echoing PBX9501 with HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) grains and Estane binder. Five cases, two graded void distributions from 1% to 10% and 10% to 1% by volume along the length of the sample, and three uniform distributions matching the lowest (1%), average (5.5%), and highest (10%) void densities are considered. An Arrhenius reaction burn model is used to account for the chemical kinetics of HMX. Different detonation behaviors are obtained from the same graded sample when impact loading is from 1% void end and from the 10% void end as well as from the uniform cases. The SDT (shock to detonation transition) behaviors are analyzed in terms of the run distance, the time duration and shock velocity changes over the SDT process. The computational results are presented in the context of available experimental data for PBX9501 with which agreement is obtained through a parametric study. Overall, it is shown that gradients in microstructures of PBX can lead to SDT behaviors different or not obtainable from microstructures without gradients, thereby offering a mechanism for designing and tailoring new materials. [ABSTRACT FROM AUTHOR]

Self-supported NiCo 2 O 4 @Ni 1.18 S core-shell nanocomposite were synthesized on nickel foams by uniform growth Ni 1.18 S nanosheets encircling NiCo 2 O 4 nanoneedles. Characterization results demonstrate that NiCo 2 O 4 @Ni 1.18 S core-shell nanocomposite have significant advantages in one - and two-dimensional nanostructure coordination structure, with richer REDOX active sites and more energy storage paths. Density functional theory (DFT) calculations results indicate that the surficial adsorption energy with OH− ions is enhanced in NiCo 2 O 4 @ Ni 1.18 S nanocomposite, thereby facilitating the reversible redox reaction kinetics and the electrochemical activity. As a result, self-supported NiCo 2 O 4 @Ni 1.18 S core-shell nanocomposite exhibit excellent energy-storage properties, i.e.: the specific charge capacity of 3158 F g−1 at 1 A g−1, high rate performance of 52.3 % from 1 A g−1 to 5 A g−1, and the 81.25 % capacity retention rate after 5000 cycles. Especially, it should be pointed out that the hybrid supercapacitors assembled from self-supported NiCo 2 O 4 @Ni 1.18 S core-shell nanocomposite and activated carbon present the wide voltage window (0–1.6 V), high energy density of 100.3 Wh kg−1 at power density of 177 W kg−1 and prospective commercial consideration. These facts fully prove the practical feasibility of self-supported NiCo 2 O 4 @Ni 1.18 S core-shell nanocomposite in advanced energy-storage facilities. [Display omitted] • NiCo 2 O 4 @Ni 1.18 S core-shell nanocomposite are constructed by hydrothermal-calcination-electrodeposition method. • This core-shell nanostructure has the structural advantages and composition complementariness. • Hybrid supercapacitors are assemled based on core-shell NiCo 2 O 4 @Ni 1.18 S and active carbon. • Hybrid device is promising for smart watches, electric vehicles, and wearable electronics, etc. [ABSTRACT FROM AUTHOR]

Green hydrogen is a crucial element in the hydrogen value chain, encompassing hydrogen production, transportation, storage, and application. The production of green hydrogen via NaBH 4 hydrolysis (SBH) entails a high cost. However, the fast kinetics of this process with a catalyst compensate for the substantial cost, especially in specific applications, such as local or intermittent use. Silver is known for its excellent catalytic properties. Its high catalytic activity is a key factor in achieving efficient hydrogen generation from (SBH). In this study, a nanocomposite catalyst composed of silver nanoparticles (AgNPs), CoFe 2 O 4 , and carbon nanotubes (CNT) was investigated to demonstrate an effective catalyst design approach to achieve enhanced hydrogen generation performance. The H 2 production rate in the presence of Ag-based/CoFe 2 O 4 –CNT was 320 mL min−1 g−1, and the apparent activation energy was 14.7 kJ mol−1, superior to that of Ag-based catalysts reported in the literature. Analyses of the observed outcomes revealed that the CNT was decorated with well-dispersed AgNPs and CoFe 2 O 4 nanoparticles. The synergistic effects of AgNPs, CoFe 2 O 4 , and CNT were demonstrated by analyzing the kinetic behaviour of each component based on systematic comparisons. Furthermore, the paramagnetic property of CoFe 2 O 4 enables harvesting of the catalyst using an external magnetic field, and it was verified that the reactivity of the collected catalyst was maintained throughout seven successive cycles. The outstanding catalytic performance of Ag/CoFe 2 O 4 – CNT should be attributed to the uniform dispersion of nanoparticles on the CNT surface. Furthermore, our key approach for developing efficient Ag-based carbon advanced catalysts for SBH in the future is to ensure their suitability for industrial applications. Graphical illustration for the hydrogen production by hydrolysis process. [Display omitted] • A magnetic Ag/CoFe 2 O 4 -carbon nanotube nanocomposite was designed and synthesized. • Highly dispersed CoFe 2 O 4 and AgNPs are evenly embedded on the CNT. • Reaction kinetics followed during hydrogen production under different experimental conditions have been investigated. • The ACC catalyst demonstrated high activity, good recyclability, and low activation energy. [ABSTRACT FROM AUTHOR]

This work reported the influence of laser surface melting (LSM) pretreatment on the growth behavior, electrical insulation and corrosion resistance of plasma electrolytic oxidation (PEO) film on 6061 aluminum alloy. It is found that the LSM pretreatment refines the surface structure of original Al metal, generating defects that store excessive energy, thereby enhancing reaction kinetics and phase transition during the PEO process. By LSM pretreatment, uniform electrical discharge and film growth can be obtained, resulting in fewer defects and lower porosity in PEO layers. Additionally, a large amount of columnar crystals comprising of SiO 2 phase are observed, which transformed from the SiO 3 2− deposited on the surface, and the LSM pretreatment significantly improves the electrical insulation, corrosion resistance, and substrate adhesion of following PEO layer. Under the same PEO treatment duration, the breakdown voltage of coating increased by 100 V, and icorr decreased from 3.26 × 10−4 to 9.13 × 10−6 A cm−2. It is expected that the combination of LSM and PEO processes can not only enhance the surface properties of Al metal, but also expand the practical application of aluminum alloy in high-power electronic devices and related fields. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] Photoelectrochemical (PEC) organic transformation at the anode coupled with cathodic H 2 generation is a potentially rewarding strategy for efficient solar energy utilization. Nevertheless, achieving the full conversion of organic substrates with exceptional product selectivity remains a formidable hurdle in the context of heterogeneous catalysis at the solid/liquid interface. Here, we put forward a quasi-homogeneous catalysis concept by using the reactive oxygen species (ROS), such as ·OH, H 2 O 2 and SO 4 •− , as a charge transfer mediator instead of direct heterogeneous catalysis at the solid/liquid interface. In the context of glycerol oxidation, all ROS exhibited a preference for first-order reaction kinetics. These ROS, however, showcased distinct oxidation mechanisms, offering a range of advantages such as ∼ 100 % conversion ratios and the flexibility to tune the resulting products. Glycerol oxidative formic acid with Faradaic efficiency (FE) of 81.2 % was realized by the H 2 O 2 and ·OH, while SO 4 •− was preferably for glycerol conversion to C 3 products like glyceraldehyde and dihydroxyacetone with a total FE of about 80 %. Strikingly, the oxidative coupling of methane to ethanol was successfully achieved in our quasi-homogeneous system, yielding a remarkable production rate of 12.27 μmol h−1 and an impressive selectivity of 92.7 %. This study is anticipated to pave the way for novel approaches in steering solar-driven organic conversions by manipulating ROS to attain desired products and conversion ratios. [ABSTRACT FROM AUTHOR]

Starch retrogradation is important in controlling many properties of starch-rich foods, while many crucial issues remain to be answered in this field. This review for the first time summarized recent understandings on starch retrogradation property, especially from the kinetics and molecular perspectives. Consecutive reaction kinetics (CR) model was recently proposed to help understand nucleation and crystal growth steps, which are critical in determining the overall retrogradation rate. By applying CR model, relations between starch fine molecular structures and retrogradation property have been revealed. Food ingredients, e.g. sugars, salts, proteins, lipids, polyphenols, and various non-starch polysaccharides, all influence starch retrogradation via different mechanisms. These new insights were comprehensively discussed in this review, aiming to help the development of functional foods with both preferable texture and nutrition property, through a better manipulation of starch retrogradation property during food processing. [ABSTRACT FROM AUTHOR]

Pressure solution is inferred to be a significant contributor to sediment compaction and lithification, especially in carbonate sediments. For a sediment deforming primarily by pressure solution, the compaction rate should be directly related to the rate of calcite dissolution, transport along grain contacts, and calcite reprecipitation. Previous experimental work has shown that there is evidence that deformation in wet calcite grain packs is consistent with control by pressure solution, but considerable ambiguity remains regarding the rate limiting mechanism. We present the results of laboratory compaction experiments designed to directly measure calcite dissolution and precipitation rates (recrystallization rates) concurrently with strain rate to test whether measured rates are consistent with predicted rates both in absolute magnitude and time evolution. Recrystallization rates are measured using trace element chemistry (Sr/Ca, Mg/Ca) and isotopes (87Sr/86Sr) of fluids flowing slowly through a compacting grain pack as it is being triaxially compressed. Imaging techniques are used to characterize the grain contacts and strain effects in the post-experiment grain pack. Our data show that calcite recrystallization rates calculated from all three geochemical parameters are in approximate agreement and that the rates closely track strain rate. The geochemically inferred rates are close to predicted rates in absolute magnitude. Uncertainty in grain contact dimensions makes distinguishing between surface reaction control and diffusion control difficult. Measured reaction rates decrease faster than predicted from standard pressure solution creep flow laws. This inconsistency may indicate that calcite dissolution rates at grain contacts are more complex, and more time-dependent, than suggested by geometric models designed to predict grain contact stresses. [ABSTRACT FROM AUTHOR]

The Ag-PSi@SiC@C electrode features a substantially higher lithium-ion mobility of 2.4 × 10−9 cm2·s−1, which is significantly greater than the mobility of silicon at 5.1 × 10−12 cm2·s−1. With this anode, the half-cell exhibits excellent rate capability and cycling stability at a current density of 2.0 A/g, with a capacity of 1321.7 mAh/g that is maintained over 200 cycles, dropping only to 962.6 mAh/g. [Display omitted] Silicon-based material is regarded as one of the most promising anodes for next-generation high-performance lithium-ion batteries (LIBs) due to its high theoretical capacity and low cost. Harnessing silicon carbide's robustness, we designed a novel porous silicon with a sandwich structure of carbon/silicon carbide/Ag-modified porous silicon (Ag-PSi@SiC@C). Different from the conventional Si C interface characterized by a frail connection, a robust dual covalent bond configuration, dependent on Si C and Si O C, has been successfully established. Moreover, the innovative sandwich structure effectively reduces detrimental side reactions on the surface, eases volume expansion, and bolsters the structural integrity of the silicon anode. The incorporation of silver nanoparticles contributes to an improvement in overall electron transport capacity and enhances the kinetics of the overall reaction. Consequently, the Ag-PSi@SiC@C electrode, benefiting from the aforementioned advantages, demonstrates a notably elevated lithium-ion mobility (2.4 * 10−9 cm2·s−1), surpassing that of silicon (5.1 * 10−12 cm2·s−1). The half-cell featuring Ag-PSi@SiC@C as the anode demonstrated robust rate cycling stability at 2.0 A/g, maintaining a capacity of 1321.7 mAh/g, and after 200 cycles, it retained 962.6 mAh/g. Additionally, the full-cell, featuring an Ag-PSi@SiC@C anode and a LiFePO 4 (LFP) cathode, exhibits outstanding longevity. Hence, the proposed approach has the potential to unearth novel avenues for the extended exploration of high-performance silicon-carbon anodes for LIBs. [ABSTRACT FROM AUTHOR]

[Display omitted] Exploiting highly efficient, cost-effective and stable electrocatalysts is key to decreasing hydrogen evolution reaction (HER) kinetics energy barrier. Herein, the alkaline HER kinetics energy barrier can greatly reduce by the joint strategies of the cation vacancy and heterostructure engineering, which is seldom explored and remains ambiguous. In this study, an efficient and stable copper foam-supported Cu 3 P-CoP heterostructure electrocatalyst with cation vacancy defects (defined as Cu 3 P-CoP-V Al /CF) was designed for HER via the successive coprecipitation, electrodeposition, alkali etching and phosphorization treatments. As anticipated, the as-obtained Cu 3 P-CoP-V Al /CF electrocatalyst reveals a remarkable catalytic activity for HER with a low overpotential of 205 mV at a current density of 100 mA·cm−2, a high turnover frequency value of 1.05 s−1 at an overpotential of 200 mV and a small apparent activation energy (E a) of 9 kJ·mol−1, while shows superior long-term stability at large current densities of 100 and 240 mA·cm−2. Systematic experiment and characterization data demonstrate that the formed cation vacancy could optimize the E a , leading to the decrease of the kinetic barriers of Cu 3 P-CoP/CF heterostructure, as well as the established heterogeneous interface induced a synergistic effect between biphasic components on boosting the kinetics toward HER. The results of density functional theory disclose that the synergistic effect of Cu 3 P-CoP heterostructure could decrease the energy barrier and optimize Gibbs free energy of hydrogen adsorption, resulting in the enhancement of intrinsic catalytic activity of Cu 3 P-CoP-V Al /CF. More significantly, the alkali-cell assembled by Cu 3 P-CoP-V Al /CF (cathode) and RuO 2 /CF (anode) behaves outstanding water splitting performance, delivering a current density of 10 mA·cm−2 at a relatively small applied voltage of 1.58 V, along with encouraging long-term durability. In addition, the alkaline Zn-H 2 O battery with Cu 3 P-CoP-V Al /CF as the cathode has been fabricated for the simultaneous generation of electricity and hydrogen, which displays a large power density of up to 4.1 mW·cm−2. The work demonstrates that rational strategy for the design of competent electrocatalysts can effectively accelerate the kinetics of HER, which supplies valuable insights for practical applications in overall water splitting. [ABSTRACT FROM AUTHOR]

This work combines the nanoconfined material with the air-breathing gas diffusion electrode equips a wide practical range of applications for the synthesis of high-yield H 2 O 2 and upgrading of H 2 O 2 products. [Display omitted] • Yolk-shell SnS 2 @CSs Z-scheme nanoreactor is controllably synthesized. • Hydrogen peroxide production is increased through the nano-confinement effect. • Continuous hydrophobic layers allow air to spontaneously diffuse into the AGPE. • The photoelectrode has a good reusability and stability for activation of O 2 /H 2 O. • Hydrogen peroxide is produced under neutral condition media. The diffusion and adsorption properties of the O 2 /H 2 O corpuscles at active sites play a crucial role in the fast photo-electrocatalytic reaction of hydrogen peroxide (H 2 O 2) production. Herein, SnS 2 nanosheets with abundant interfacial boundaries and large specific areas are encapsulated into hollow mesoporous carbon spheres (CSs) with flexibility, producing a yolk-shell SnS 2 @CSs Z-scheme photocatalyst. The nanoconfined microenvironment of SnS 2 @CSs could enrich O 2 /H 2 O in catalyst cavities, which allows sufficient internal O 2 transfer, improving the surface chemistry of catalytic O 2 to O 2 − conversion and increasing reaction kinetics. By shaping the mixture of SnS 2 @CSs and polytetrafluoroethylene (PTFE) on carbon felt (CF) using the vacuum filtration method, the natural air-breathing gas diffusion photoelectrode (AGPE) was prepared, and it can achieve an accumulated concentration of H 2 O 2 about 12 mM after a 10 h stability test from pure water at natural pH without using electrolyte and sacrificial agents. The H 2 O 2 product is upgraded through one downstream route of conversion of H 2 O 2 to sodium perborate. The improved H 2 O 2 production performance could be ascribed to the combination of the confinement effect of SnS 2 @CSs and the rich triple phase interfaces with the continuous hydrophobic layer and hydrophilic layer to synergistically modulate the photoelectron catalytic microenvironment, which enhanced the transfer of O 2 mass and offered a stronger affinity to oxygen bubbles. The strategy of combining the confined material with the air-breathing gas diffusion electrode equips a wide practical range of applications for the synthesis of high-yield hydrogen peroxide. [ABSTRACT FROM AUTHOR]

[Display omitted] • Large area, 2D β-Ni(OH) 2 , < 3 nm thin nanosheets synthesized at water–air interface. • Device shows 820 mAh.cm−3 capacity with 70% retention after 30,000 cycles. • Device achieved ultrahigh energy density of 0.33 Wh.cm−3 at 275.86 W.cm −3. • β- Ni(OH) 2 shows enhanced OER activity η 10 :308 mV with Tafel value of 42 mV dec-1. • After charge storage & OER, XPS analysis confirms structural stability of the film. Bifunctional electrode materials are highly desirable for meeting increasing global energy demands and mitigating environmental impact. However, improving the atom-efficiency, scalability, and cost-effectiveness of storage systems, as well as optimizing conversion processes to enhance overall energy utilization and sustainability, remains a significant challenge for their application. Herein, we devised an optimized, facile, economic, and scalable synthesis of large area (cm2), ultrathin (∼2.9 ± 0.3 nm) electroactive nanosheet of β-Ni(OH) 2, which acted as bifunctional electrode material for charge storage and oxygen evolution reaction (OER). The β-Ni(OH) 2 nanosheet electrode shows the volumetric capacity of 2.82 Ah.cm−3(0.82 µAh.cm−2) at the current density of 0.2 mA.cm −2. The device shows a high capacity of 820 mAh.cm−3 with an ultrahigh volumetric energy density of 0.33 Wh.cm−3 at 275.86 W.cm −3 along with promising stability (30,000 cycles). Furthermore, the OER activity of ultrathin β-Ni(OH) 2 exhibits an overpotential (η 10) of 308 mV and a Tafel value of 42 mV dec-1 suggesting fast reaction kinetics. The mechanistic studies are enlightened through density functional theory (DFT), which reveals that additional electronic states near the Fermi level enhance activity for both capacitance and OER. [ABSTRACT FROM AUTHOR]

As an anode for sodium-ion batteries, CuInS 2 @PPy exhibits excellent rate performance and cycling stability due to the synergism of combinational intercalation-conversion-intercalation reaction mechanism and the high conductivity of the PPy coating layer. [Display omitted] Polypyrrole-coated CuInS 2 (CuInS 2 @PPy) composite was prepared through the chemical vapor transport method and subsequent in situ polymerized coating strategy. In this unique nanoarchitecture, the PPy coating layer plays a crucial role in improving the conductivity of the composite, suppressing the volume change of CuInS 2 , and maintaining the structural integrity of electrode material upon cycling. In addition, the electrochemical reaction mechanism and kinetics of CuInS 2 @PPy were investigated in-depth. Benefitting from the synergism of its combinational intercalation-conversion-intercalation reaction mechanism and the high conductivity of the PPy coating layer, CuInS 2 @PPy electrode exhibits superior rate capability and cycling stability for sodium-ion batteries, with a capacity of 404.8 mA h g−1 at 4 A g−1 over 2500 cycles. [ABSTRACT FROM AUTHOR]

[Display omitted] Aqueous zinc-ion batteries (AZIBs) are competitive alternatives for large-scale energy-storage devices owing to the abundance of zinc and low cost, high theoretical specific capacity, and high safety of these batteries. High-performance and stable cathode materials in AZIBs are the key to storing Zn2+. Manganese-based cathode materials have attracted considerable attention because of their abundance, low toxicity, low cost, and abundant valence states (Mn2+, Mn3+, Mn4+, and Mn7+). However, as a typical cathode material, birnessite-MnO 2 (δ-MnO 2) has low conductivity and structural instability. The crystal structure may undergo severe distortion, disorder, and structural damage, leading to severe cyclic instability. In addition, its energy-storage mechanism is still unclear, and most of the reported manganese oxide-based materials do not have excellent electrochemical performance. Herein, we propose a copper-doped Cu 0.05 K 0.11 Mn 0.84 O 2 ·0.54H 2 O (Cu 2 -KMO) cathode, which exhibits a large interlayer spacing, a stable structure, and accelerated reaction kinetics. This cathode was prepared using a simple hydrothermal method. The AZIB assembled using Cu 2 -KMO showed high specific capacity (600 mA h g−1 at 0.1 A g−1 after 75 cycles). The dissolution-deposition energy storage mechanism of Cu-KMO in AZIBs with double electron transfer was revealed using ex situ tests. The good electrochemical performance of the Cu 2 -KMO cathode fabricated by the doping strategy in this study provides ideas for the subsequent preparation of manganese dioxide using other strategies. [ABSTRACT FROM AUTHOR]

The laser-regulated mixed-phase TiO 2 efficiently enhances the hydrogenation or hydroxylization of nitrogen to form NH*/NOxOH*, thereby promoting electrochemical overall nitrogen fixation. [Display omitted] • Laser synthesis has achieved the fabrication of TiO 2 integrated electrodes with controllable phase sites. • The optimized mixed-phase TiO 2 can serve as both anode and cathode, achieving good nitrogen reduction and oxidation activity. • The rutile phase promotes nitrogen adsorption activation, while the anatase phase provides protons and reactive oxygen species. • A dual-electrode coupled system constructing by mixed-phase TiO 2 achieves a breakthrough in overall electrocatalytic nitrogen fixation. Traditional oxide electrocatalytic materials encounter significant challenges associated with sluggish reaction kinetics and formidable energy barriers for NH intermediates formation in electrocatalytic nitrogen fixation. The implementation of phase control emerges as an effective strategy to address these challenges. Herein, leveraging the energy localization of laser, this work achieved precise phase control of TiO 2. In the optimized material system, the rutile phase TiO 2 facilitates nitrogen adsorption, while the anatase phase TiO 2 provides proton sources and active oxygen species. The synergistic effect of the two phases effectively enhances the electrocatalytic activity for nitrogen reduction and oxidation, with an ammonia yield reaching ∼22.3 μg h-1 cm-2 and a nitrate yield reaching ∼60.9 μg h-1 cm-2. Furthermore, a coupled dual-electrode system with mixed-phase titanium dioxide as both the anode and cathode successfully achieved a breakthrough in electrochemical overall nitrogen fixation. This laser precision control strategy for manipulating phase sites lays the groundwork for designing efficient catalysts for energy conversion and even energy storage nanomaterials. [ABSTRACT FROM AUTHOR]

Heteroatom Ni doping strategy was employed to tune the electronic conductivity of FeS 2 with rapid Na+ accessibility in sodium ion battery. As expected, Ni-FeS 2 @NC delivered high specific capacity and superior rate performance. [Display omitted] Iron sulfides (FeS 2) are promising anode materials for sodium ion batteries (SIBs); however, their inferior electronic conductivity, large volume swelling, and sluggish sodium ion diffusion kinetics lead to unsatisfactory rate performance and cycling durability. Heteroatom doping plays a crucial role in modifying the physicochemical properties of FeS 2 anodes to enhance its sodium storage. Herein, ultra-fine Ni-doped FeS 2 nanocrystals derived from a metal–organic framework (MOF) and in-situ anchored on a nitrogen doped carbon skeleton (Ni-FeS 2 @NC) are proposed to enhance both structural stability and reaction kinetics. Material characterization, electrochemical performance, and kinetics analysis demonstrate the critical role of Ni doping in sodium storage, particularly in accelerating Na+ diffusion efficiency. The N-doped carbon derived from the MOF can buffer the volume expansion and enhance the structural stability of electrode materials during sodiation/desodiation processes. As expected, Ni-FeS 2 @NC exhibits a high reversible capacity of 656.6 ± 65.1 mAh g−1 at 1.0 A g−1 after 200 cycles, superior rate performance (308.8 ± 6.0 mAh g−1 at 10.0 A g−1), and long-term cycling durability over 2000 cycles at 1.0 A g−1. Overall, this study presents an effective approach for enhancing the sodium storage performance and kinetics of anode materials for high efficiency SIBs. [ABSTRACT FROM AUTHOR]

A mechanism for carbon deposition and its impact on the reaction kinetics of Methane Dry Reforming (MDR) using Rhodium‐based catalysts is presented. By integrating Raman spectroscopy with kinetic analysis in an operando‐annular chemical reactor under strict chemical conditions, we discovered that carbon deposition on a Rh/α‐Al2O3 catalyst follows a nucleation‐growth mechanism. The dynamics of carbon aggregates at the surface is found to be ruled by the CO2/CH4 ratio and the inlet CH4 concentration. The findings elucidate the spatiotemporal development of carbon aggregates on the catalyst surface and their effects on catalytic performance. Furthermore, the proposed mechanism for carbon formation shows that the influence of CO2 on MDR kinetics is an indirect result of carbon accumulation over time frames exceeding the turnover frequency, thus reconciling conflicting reports in the literature regarding CO2′s kinetic role in MDR. [ABSTRACT FROM AUTHOR]