Elementary Mechanisms Research Articles

Entropy Engineering of 2D Materials.

Entropy, a measure of disorder or uncertainty in the thermodynamics system, has been widely used to confer desirable functions to alloys and ceramics. The incorporation of three or more principal elements into a single sublattice increases the entropy to medium and high levels, imparting these materials a mélange of advanced mechanical and catalytic properties. In particular, when scaling down the dimensionality of crystals from bulk to the 2D space, the interplay between entropy stabilization and quantum confinement offers enticing opportunities for exploring new fundamental science and applications, since the structural ordering, phase stability, and local electronic states of these distorted 2D materials get significantly reshaped. During the last few years, the large family of high-entropy 2D materials is rapidly expanding to host MXenes, hydrotalcites, chalcogenides, metal-organic frameworks (MOFs), and many other uncharted members. Here, the recent advances in this dynamic field are reviewed, elucidating the influence of entropy on the fundamental properties and underlying elementary mechanisms of 2D materials. In particular, their structure-property relationships resulting from theoretical predictions and experimental findings are discussed. Furthermore, an outlook on the key challenges and opportunities of such an emerging field of 2D materials is also provided.

Investigating the Thermal Decomposition of BP into B12P2: Experimental Insights and Kinetic Modelling at High Temperatures

This study investigates the thermal decomposition of BP into B12P2, with a particular focus on the heterogeneous solid-gas mechanism involving BP powders synthesized via self-propagating high temperature reactions. Various techniques, including XRD, TGA, SEM, TEM, EELS and SAED, were combined to examine morphological and structural changes at different temperatures. The results reveal an ignition temperature for decomposition at 1120°C, beyond which BP grains undergo fragmentation into smaller particles, accompanied by the release of phosphorous gases (P2(g), P4(g)). Additionally, Rietveld refinements on thermally treated powders facilitated the determination of advancement rate values of the decomposition reaction under different isothermal conditions. Based on these kinetic data obtained at 1300°C, a one-process nucleation-growth model with instantaneous nucleation and anisotropic growth has be established. In particular, the law, which describes the process for a spherical grain with inward development and a reaction occurring at the internal interface as the step determining the rate, displayed a strong correlation coefficient, offering novel insights into the kinetic evolution of the BP to B12P2 conversion. These results contribute to a deeper understanding of the thermal decomposition process and its underlying elementary mechanisms.

Hydrogen Electrode Reactions in Energy-Related Electrocatalysis Systems.

Hydrogen electrode reactions, including hydrogen evolution reactions and hydrogen oxidation reactions, are fundamental and crucial within aqueous electrochemistry. Particularly in energy-related electrocatalysis processes, there is a consistent involvement of hydrogen-related electrochemical processes, underscoring the need for in-depth study. This review encompasses significant reports, delving into elementary steps and reaction mechanisms of hydrogen electrode reactions, as well as catalyst design strategies. In addition, we focus on the application of hydrogen electrode reaction mechanism in different energy-related electrocatalytic reactions, and the significance of the promotion and suppression of reaction kinetics in different reaction systems. It thoroughly elucidated the significance of these reactions and the need for a deeper understanding, offering a novel perspective for the future development of this field.

Cobalt-Catalyzed Enantioselective Reductive Arylation, Heteroarylation, and Alkenylation of Michael Acceptors via an Elementary Mechanism of 1,4-Addition.

Cobalt complexes with chiral quinox ligands effectively promote the enantioselective conjugate addition of enones using aryl, heteroaryl, and alkenyl halides and sulfonates. Additionally, a cobalt complex with a strongly donating diphosphine, BenzP*, successfully catalyzes the asymmetric reductive arylation and alkenylation of α,β-unsaturated amides. Both catalytic systems show broad scopes and tolerance of sensitive functional groups. Both reactions can be scaled up with low loadings of cobalt catalysts. Experimental results and density functional theory (DFT) calculations suggest a new mechanism of elementary 1,4-addition of aryl cobalt(I) complexes.

Numerical investigation on the hydrogen removal capability of various catalytic elements in PARs

As an essential part of hydrogen removal system in nuclear power plants, PARs could effectively eliminate released hydrogen and prevent potential hydrogen combustion during severe accidents. Serving as a basic composition in the catalytic section of PARs, catalytic element has a direct influence on the hydrogen removal capability of the PAR device. The CFD software STAR-CCM+ was utilized to develop models of catalytic channels containing three common catalytic elements (including catalytic plates, catalytic cylinders, and catalytic spheres). The elementary reaction mechanism was employed as the reaction kinetics model to define the chemical reaction process. This paper aims to evaluate the hydrogen removal capability of the catalytic elements in same operating conditions and analyze important factors for designing the structure of catalytic elements. All the catalytic surface area of catalytic elements was set to 0.045 m2 and inlet boundary conditions were settled identically. Our findings show that catalytic sphere exhibits the best hydrogen removal capability, which is attributed to the large lower half catalytic surface area of spheres. Catalytic plate with a lower height also demonstrates excellent hydrogen removal capability because of the presence of a larger catalytic area in the leading section. However, the hydrogen removal capability of catalytic cylinder is affected by the boundary layer separation vortex. A noticeable decrease in reaction rate occurs on the lower part of the sidewall surface, especially in the catalytic cylinder with a larger radius. In the structure design of catalytic elements, enlarging the catalytic surface area in the leading section and avoiding boundary layer separation on the catalytic surface are essential to further improve the hydrogen removal capability.

Yield stress anomaly and creep of single crystal Ni-base superalloys – Role of particle size

In the present work we subject the single crystal Ni-base superalloy ERBO1 (CMSX 4 type) to constant strain rate (CSR) and creep testing at temperatures between 1023 and 1223 K. Three material states are considered which have similar particle volume fractions >60% but differ in γ′-particle sizes (material states S, M and L of particle sizes: 240, 390 and 540 nm). In constant strain rate testing, a yield stress anomaly is observed for all three material states, with a yield stress maximum at 1073 K. This increase of strength with increasing temperature is not observed during creep testing at significantly lower deformation rates in this low temperature high stress creep regime, where different elementary deformation mechanisms govern CSR and creep behavior. In contrast, in the low stress high temperature creep regime, stress/strain rate data pairs from CSR creep tests both show decreasing strength with increasing temperature. It is found that in both types of tests the material state M shows the highest strength (highest yield stress and lowest creep rate). This can be rationalized based on a scenario where both, γ-channel and γ′-particle dislocation activities are important. Diffraction contrast transmission electron microscopy is used to study the relevant elementary deformation processes. Details of dislocation arrangements are discussed with a special focus on the role of Kear Wilsdorf (KW) locks, γ′-particle shearing by superlattice stacking faults (extrinsic and intrinsic) and dislocation climb.

Coherent Transient Localization Mechanism of Interchain Exciton Transport in Regioregular P3HT: A Quantum-Dynamical Study.

Transient localization has been proposed as a transport mechanism in organic materials, for both charge carriers and excitons. Here, we characterize a quantum coherent transient localization mechanism using full quantum simulations of an H-aggregated model system representative of regioregular poly(3-hexylthiophene) (rrP3HT). A Frenkel-Holstein Hamiltonian parametrized from first principles is considered, including local high-frequency modes and anharmonic, site-correlated interchain modes. Quantum-dynamical calculations are carried out using the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method for a 13-site system with 195 vibrational modes, under periodic boundary conditions. It is shown that temporary localization of exciton polarons alternates with resonant transfer driven by interchain modes. While the transport process is mainly determined by exciton-polarons at the low-energy band edge, persistent coupling with the excitonic manifold is observed, giving rise to a nonadiabatic excitonic flux. This elementary transport mechanism remains preserved for limited static disorder and gives way to Anderson localization when the static disorder becomes dominant.

Segregation-induced strength anomalies in complex single-crystalline superalloys

Pushing the maximum service temperature of aircraft engines and industrial gas turbines is the major pathway to improve their energy efficiency and reduce CO2 emissions. This maximum is mostly limited by the temperature capability of key-component materials, including superalloys. In this alloy class, segregation of elements facilitates plastic deformation and is generally considered to cause softening during high-temperature deformation. Here, we show that segregation-assisted processes can also lead to strengthening and induce an anomalous increase of the yield strength. Atomic-resolution transmission electron microscopy and density functional theory calculations reveal a segregation-assisted dissociation process of dislocations at precipitate-matrix interfaces in combination with atomic-scale reordering processes. These processes lead to an inhibition of athermal deformation mechanisms and a transition to stacking fault shearing, which causes the strengthening effect. Unraveling these elementary mechanisms might guide a mechanism-based alloy design of future superalloys with enhanced high-temperature capabilities.

On-chip very low strain rate rheology of amorphous olivine films

Recent observations made by the authors revealed the activation of stress induced amorphization and sliding at grain boundary in olivine [1], a mechanism which is expected to play a pivotal role in the viscosity drop at the lithosphere-asthenosphere boundary and the brittle-ductile transition in the lithospheric mantle. However, there is a lack of information in the literature regarding the intrinsic mechanical properties and the elementary deformation mechanisms of this material, especially at time scales relevant for geodynamics. In the present work, amorphous olivine films were obtained by pulsed laser deposition (PLD). The mechanical response including the rate dependent behavior are investigated using a tension-on-chip (TOC) method developed at UCLouvain allowing to perform creep/relaxation tests on thin films at extremely low strain rates. In the present work, strain rate down to 10−12 s−1 was reached which is unique. High strain rate sensitivity of 0.054 is observed together with the activation of relaxation at the very early stage of deformation. Furthermore, digital image correlation (DIC), used for the first time on films deformed by TOC, reveals local strain heterogeneities. The relationship between such heterogeneities, the high strain rate sensitivity and the effect of the electron beam in the scanning electron microscope is discussed and compared to the literature.

Kinetic Modeling of the Direct Dimethyl Ether (DME) Synthesis over Hybrid Multi-Site Catalysts

This paper deals with the proposition of a kinetic model for the direct synthesis of DME via CO2 hydrogenation in view of the necessary optimization of the catalytic system, reactor design, and process strategy. Despite the fact that DME synthesis is typically treated as a mere combination of two separated catalytic steps (i.e., methanol synthesis and methanol dehydration), the model analysis is now proposed by taking into account the improvements related to the process running over a hybrid catalyst in a rational integration of the two catalytic steps, with boundary conditions properly assumed from the thermodynamics of direct DME synthesis. Specifically, the CO2 activation step at the metal–oxide interface in the presence of ZrO2 has been described for the first time through the introduction of an ad hoc mechanism based on solid assumptions from inherent studies in the literature. The kinetic modeling was investigated in a tubular fixed-bed reactor operating from 200 to 260 °C between 1 and 50 bar as a function of a gas hourly space velocity ranging from 2500 to 60,000 NL/kgcat/h, in a stoichiometric CO2/H2 feed mixture of 1:3 v/v. A well-detailed elementary mechanism was used to predict the CO2 conversion rate and identify the key reaction pathways, starting with the analysis of the implicated reactions and corresponding kinetic mechanisms and expressions, and finally estimating the main parameters based on an appropriate modeling of test conditions.

Infrared Nanoimaging of Hydrogenated Perovskite Nickelate Memristive Devices.

Solid-state devices made from correlated oxides, such as perovskite nickelates, are promising for neuromorphic computing by mimicking biological synaptic function. However, comprehending dopant action at the nanoscale poses a formidable challenge to understanding the elementary mechanisms involved. Here, we perform operando infrared nanoimaging of hydrogen-doped correlated perovskite, neodymium nickel oxide (H-NdNiO3, H-NNO), devices and reveal how an applied field perturbs dopant distribution at the nanoscale. This perturbation leads to stripe phases of varying conductivity perpendicular to the applied field, which define the macroscale electrical characteristics of the devices. Hyperspectral nano-FTIR imaging in conjunction with density functional theory calculations unveils a real-space map of multiple vibrational states of H-NNO associated with OH stretching modes and their dependence on the dopant concentration. Moreover, the localization of excess charges induces an out-of-plane lattice expansion in NNO which was confirmed by in situ X-ray diffraction and creates a strain that acts as a barrier against further diffusion. Our results and the techniques presented here hold great potential for the rapidly growing field of memristors and neuromorphic devices wherein nanoscale ion motion is fundamentally responsible for function.

The evolution of peace (and war) is driven by an elementary social interaction mechanism.

Here we revise Glowacki's model by proposing a simple and empirically tested mechanism that is applicable to a comprehensive set of social interactions. This parsimonious mechanism accounts for the choice of both cooperative and peaceful alternatives and explains when each choice benefits the interacting parties. It is proposed that this mechanism is key to the evolution of both peace and conflict.

Shape equilibria of vesicles with rigid planar inclusions.

Motivated by recent studies of two-phase lipid vesicles possessing 2D solid domains integrated within a fluid bilayer phase, we study the shape equilibria of closed vesicles possessing a single planar, circular inclusion. While 2D solid elasticity tends to expel Gaussian curvature, topology requires closed vesicles to maintain an average, non-zero Gaussian curvature leading to an elementary mechanism of shape frustration that increases with inclusion size. We study elastic ground states of the Helfrich model of the fluid-planar composite vesicles, analytically and computationally, as a function of planar fraction and reduced volume. Notably, we show that incorporation of a planar inclusion of only a few percent dramatically shifts the ground state shapes of vesicles from predominantly prolate to oblate, and moreover, shifts the optimal surface-to-volume ratio far from spherical shapes. We show that for sufficiently small planar inclusions, the elastic ground states break symmetry via a complex variety of asymmetric oblate, prolate, and triaxial shapes, while inclusion sizes above about 8% drive composite vesicles to adopt axisymmetric oblate shapes. These predictions cast useful light on the emergent shape and mechanical responses of fluid-solid composite vesicles.

Multiphoton tandem photoredox catalysis of [Ir(dFCF3ppy)2(dtbbpy)]+ facilitating radical acylation reactions.

Photoredox catalytic radical acylation reactions, utilizing [Ir(dFCF3ppy)2(dtbbpy)]+ (IrIII) as the photocatalyst and α-keto acids as the starting substrates, have recently emerged as an attractive strategy for preparing ketone derivatives. While there is consensus on the importance of detailed mechanistic insights to maximize the formation of desired products, efforts focused on uncovering the underlying elementary mechanisms of IrIII photocatalytic radical acylation reactions are still lacking. Herein, using time-resolved spectroscopy, we observed the efficient quenching of the triplet state, 3IrIII*, via electron transfer from α-keto acids, resulting in the generatation of the reduced IrII. Subsequently, IrII rapidly transforms into a stable IrH+ species through protonation, with α-keto acid acting as a proton donor. Upon absorbing additional photon(s), IrH+ is expected to transform into IrH3, involving further hydrogenation/protonation. Emission and Fourier transform infrared (FTIR) spectroscopy, together with global analysis, identify the character of IrH3/3IrH3* and corroborate its contribution to representative radical acylation reactions (decarboxylative 1,4-addition of α-keto acids with Michael acceptors, decarboxylative coupling of α-keto acids with aryl halides, and decarboxylative cyclization of 2-alkenylarylisocyanides with α-keto acids), where IrH3/3IrH3* serves as the key species to trigger the second photoredox cycle. These results elucidate the existence and generality of the tandem photoredox catalysis mechanism for IrIII photocatalytic radical acylation reactions, providing advanced insights into the mechanism of IrIII-based photoredox processes and potentially expanding their application in the design and development of new synthetic methodologies.

Elementary and Advanced Mechanisms for Genetic Engineering in Crops

Presently, the field of plant breeding is in the genomics era, where innovative techniques are being integrated to accelerate and enhance the efficiency of breeding. Traditional plant breeding methods rely on maintaining plant germplasm with desirable agronomic traits from distinct plants produced through crosses or mutagenesis. However, advancements in genetic engineering encompass all forms of genetic modification through recombinant DNA technology (RDT) and cell fusion mechanisms. These approaches shed light on areas involving mutant organisms, DNA replication, genetic linkage resolution, genetically modified organisms (GMOs), protein sequencing, functional genomics, and computational genomics alterations in genetic engineering. The integration of structural genomics into breeding and eugenics analysis has resulted in a vast knowledge base on crop genetics, species divergence, and molecular origin of traits, as well as the evolutionary history of crop lineage from ancient ancestral species. The genomic data and advancements have proven essential in identifying rare genes, alleles, or local lesions crucial to significant agronomic traits, thereby expediting breeding cycles. This article aims to explore the potential of emerging genetic engineering technologies, including synthetic biology and genome editing, to further advance crop genetics and plant breeding.

Effect of Nitrogen Ion Diffusion Jumps in Nanometer-Sized Si3N4 Memristors Investigated by Low-Frequency Noise Spectroscopy

The elementary jumps in the electron current through conducting filaments of two nanometer-sized virtual memristor structures consisting of a contact of a conductive atomic force microscope probe to the Si3N4 layer with the thickness of 6[Formula: see text]nm deposited onto the [Formula: see text]-Si(001) conductive substrates are investigated. These structures are: (S1) the Si3N4/Si film; (S2) the Si3N4/SiO2/Si stack, a similar structure with 2[Formula: see text]nm SiO2 sublayer between the film and the substrate. Usually, such investigations are performed by the analysis of the waveform of this current with the aim of extracting the random telegraph noise (RTN). Here, we develop a new indirect method, which is based on the measurement of the spectrum of the low-frequency flicker noise in the current without extracting the RTN. We propose that the flicker noise is caused by the motion (drift/diffusion) of nitrogen ions via vacancies within and around the filament. The number of these ions is estimated by taking into account the geometrical parameters of the filament. This allows us to estimate the root mean square magnitude [Formula: see text] of the current jumps, which are caused by random jumps of nitrogen ions, and the number M of these ions. This is fundamental for understanding the elementary mechanisms of the electron current flowing through the filament and the resistive switching in memristor devices.

On the Shoulders of Giants-Reaching for Nitrogenase.

Only a single enzyme system-nitrogenase-carries out the conversion of atmospheric N2 into bioavailable ammonium, an essential prerequisite for all organismic life. The reduction of this inert substrate at ambient conditions poses unique catalytic challenges that strain our mechanistic understanding even after decades of intense research. Structural biology has added its part to this greater tapestry, and in this review, I provide a personal (and highly biased) summary of the parts of the story to which I had the privilege to contribute. It focuses on the crystallographic analysis of the three isoforms of nitrogenases at high resolution and the binding of ligands and inhibitors to the active-site cofactors of the enzyme. In conjunction with the wealth of available biochemical, biophysical, and spectroscopic data on the protein, this has led us to a mechanistic hypothesis based on an elementary mechanism of repetitive hydride formation and insertion.

Misfit and the mechanism of high temperature and low stress creep of Ni-base single crystal superalloys

The present work proposes a new elementary deformation mechanism which governs high temperature and low stress creep of single crystal superalloys (SXs), where the misfit between the γ- and the γ′-phase plays a central role. In the coherent two phase SX microstructure, there is a tendency to minimize the overall elastic strain energy. This is accomplished by the formation of dislocation networks in the γ-phase close to the γ/γ’-interfaces. The stress fields of the network dislocations and misfit stresses accommodate each other to keep the overall strain energy of the system at a minimum. Previous work has shown that dynamic recovery is associated with knitting-out reactions, where dislocations from the network shear the γ’-phase and annihilate with dislocations of opposite sign on the other side of the γ’-phase region. Due to the presence of the misfit this results in an increase of elastic strain energy which is counteracted by coupled knitting-in reactions where newly arriving γ-channel dislocations re-establish the minimum energy configuration. Here we provide microstructural evidence for knitting-out and knitting-in reactions and show that while these reactions clearly occur, dislocation network spacings stay constant. The misfit between the γ- and the γ′-phase accounts for a constant network spacing. Dislocation networks are not static but represent dynamic steady state equilibrium structures in an evolving microstructure. Knitting regular networks requires climb processes which are suggested to be rate controlling. This new view of high temperature and low stress creep mechanism of SXs allows to rationalize previous results published in the literature.

Morphological and Functional Principles Governing the Plasticity Reserve in the Cerebellum: The Cortico-Deep Cerebellar Nuclei Loop Model.

Cerebellar reserve compensates for and restores functions lost through cerebellar damage. This is a fundamental property of cerebellar circuitry. Clinical studies suggest (1) the involvement of synaptic plasticity in the cerebellar cortex for functional compensation and restoration, and (2) that the integrity of the cerebellar reserve requires the survival and functioning of cerebellar nuclei. On the other hand, recent physiological studies have shown that the internal forward model, embedded within the cerebellum, controls motor accuracy in a predictive fashion, and that maintaining predictive control to achieve accurate motion ultimately promotes learning and compensatory processes. Furthermore, within the proposed framework of the Kalman filter, the current status is transformed into a predictive state in the cerebellar cortex (prediction step), whereas the predictive state and sensory feedback from the periphery are integrated into a filtered state at the cerebellar nuclei (filtering step). Based on the abovementioned clinical and physiological studies, we propose that the cerebellar reserve consists of two elementary mechanisms which are critical for cerebellar functions: the first is involved in updating predictions in the residual or affected cerebellar cortex, while the second acts by adjusting its updated forecasts with the current status in the cerebellar nuclei. Cerebellar cortical lesions would impair predictive behavior, whereas cerebellar nuclear lesions would impact on adjustments of neuronal commands. We postulate that the multiple forms of distributed plasticity at the cerebellar cortex and cerebellar nuclei are the neuronal events which allow the cerebellar reserve to operate in vivo. This cortico-deep cerebellar nuclei loop model attributes two complementary functions as the underpinnings behind cerebellar reserve.

Development and application of a semi-detailed model for lithium-Ion battery thermal runaway chemistry

To overcome the disadvantages of detailed methodologies and existing simple methodologies for modeling lithium-ion battery thermal runaway chemistry, a semi-detailed model has been developed in the present work. This is important for mitigating battery thermal runaway. The semi-detailed model contains two parts: a ‘global part’ and an ‘elementary reaction mechanism part’. The thermal kinetics parameters of a recently published model are improved so that it can be selected for the ‘global part’ to model NCM811 (LiNi0.8Co0.1Mn0.1O2), NCM622 (LiNi0.6Co0.2Mn0.2O2), and NCM532 (LiNi0.5Co0.3Mn0.2O2). Temperature and heat release evolutions during battery thermal runaway can be obtained from the simulation of the ‘global part’. In the ‘elementary reaction mechanism part’, 53 reactions with frequency factors and activation energies have been proposed and adopted for describing flammable gas formation, lithium-ion consumption, gas phase interaction, and lithium-ion gas interaction during battery thermal runway. Detailed processes for coupling the ‘global part’ and the ‘elementary reaction mechanism part’ as well as solving the 53 reactions are developed, which is the major novelty of this work. Through the coupling of the two parts, chemical venting gas species generation and lithium-ion consumption during the transient thermal runaway process of an NCM811PC (LiNi0.8Co0.1Mn0.1O2 polycrystalline) pouch cell with nail penetration were calculated and compared with available experimental data in the literature. The comparison shows that the semi-detailed model can give correct species trends, indicating the two parts and their coupling in the semi-detailed model of the present work are reliable. The simulation results with transient venting gas chemical species provide useful insights for stopping or delaying battery thermal runaway.