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Synthesis Modeling and Kinetics of Rationally Designed Defects and Substitutions in 2D Materials.
Abstract not provided.
Graphite Oxidation Modeling
Oxidation modeling importance ASME consideration Effect on graphite properties Model Overview Numerical Model Oxidation Diffusion Reaction Kinetics Model Parameterization Example problems Editing the model Simple problem example Conclusions Coupling to stress analysis Oxidation result analysis
Progress in modeling hydrogen assisted ammonia oxidation with new experiments and a further reconciliation of the NH 3 + OH rate constant
Hydrogen-assisted oxidation of ammonia in a premixed, laminar flow tubular reactor under reducing conditions was investigated experimentally and through chemical kinetic modeling. Due to its impact on the competition for OH among ammonia and hydrogen, the rate constant for NH 3 + OH (R1) was determined through state-of-the-art theoretical kinetics calculations, employing composite energies that include the effects of higher order electronic excitations on the electronic energies along the variational reaction path and treating the limitations in the kinetics posed by the passage through a hydrogen-bonded complex. The resulting rate constant was in close agreement with the recent experimental value from Zaczek et al. (2025), settling a long-term dispute about the high-temperature value of k 1 and confirming within 20% the value previously used in modeling. The chemical kinetic model, with no other changes, captured well measured concentrations of NH 3 , H 2 , NO, and N 2 O from flow reactor oxidation of NH 3 /H 2 at slightly reducing conditions over a range of temperature (900-1350 K) and NH 3 /H 2 ratios (0.5-2.0). Comparison of the present results with reported data from a non-premixed setup indicates that for laminar flow tubular reactors, the reactor configuration may have implications for the observed H 2 consumption due to the possibility of preferential oxidation during mixing.
One-dimensional biomass fast pyrolysis model with reaction kinetics integrated in an Aspen Plus Biorefinery Process Model
A biomass fast pyrolysis reactor model with detailed reaction kinetics and one-dimensional fluid dynamics was implemented in an equation-oriented modeling environment (Aspen Custom Modeler). Portions of this work were detailed in previous publications; further modifications have been made here to improve stability and reduce execution time of the model to make it compatible for use in large process flowsheets. The detailed reactor model was integrated into a larger process simulation in Aspen Plus and was stable for different feedstocks over a range of reactor temperatures. Sample results are presented that indicate general agreement with experimental results, but with higher gas losses caused by stripping of the bio-oil by the fluidizing gas in the simulated absorber/condenser. Lastly, this integrated modeling approach can be extended to other well-defined, predictive reactor models for fast pyrolysis, catalytic fast pyrolysis, as well as other processes.
Data-driven, multi-moment fluid modeling of Landau damping
Deriving governing equations of complex physical systems based on first principles can be quite challenging when there are certain unknown terms and hidden physical mechanisms in the systems. In this work, we apply a deep learning architecture to learn fluid partial differential equations (PDEs) of a plasma system based on the data acquired from a fully kinetic model. Here, the learned multi-moment fluid PDEs are demonstrated to incorporate kinetic effect such as Landau damping. Based on the learned fluid closure, the data-driven, multi-moment fluid modeling can well reproduce all the physical quantities derived from the fully kinetic model. The calculated damping rate of Landau damping is consistent with both the fully kinetic simulation and the linear theory. The data-driven fluid modeling of PDEs for complex physical systems may be applied to improve the fluid closure and reduce the computational cost of multi-scale modeling of global systems.
Elucidating the Mechanism for the Reaction of $o$-Phthalaldehyde with Primary Amines in the Presence of Thiols
The use of o-phthalaldehyde (OPA) in combination with a thiol reagent is a common method for detecting primary amines in amino acids, peptides, and proteins. Despite its widespread use, the exact reaction mechanism has been debated since the 1980s. Here, we measure the kinetics of the reaction between OPA, alanine, and a dithiol (1,4-dithiolthreitol, DTT) as a function of pH and reagent concentration. Using these new measurements and accompanying kinetic models, we find evidence that the pH dependence of the kinetics arises from both the protonation states of alanine and DTT, the hydration state of OPA, and the unproductive equilibrium with DTT, all of which are pH-dependent. Importantly, these results support the mechanism originally proposed by Sternson [Rational design and evaluation of improved o-phthalaldehyde-like fluorogenic reagents. Anal. Biochem. 1985, 144, 233–246] and Wong [Reaction of o-phthalaldehyde with alanine and thiols: kinetics and mechanism. J. Am. Chem. Soc. 1985, 107, 6421–6422], in which the primary amine first reacts with OPA, followed by a reaction with the thiol to form the fluorescent isoindole product.
Incorporation of velocity-dependent restitution coefficient and particle surface friction into kinetic theory for modeling granular flow cooling
Kinetic theory (KT) has been successfully used to model rapid granular flows in which particle interactions are frictionless and near elastic. However, it fails when particle interactions become frictional and inelastic. For example, the KT is not able to accurately predict the free cooling process of a vibrated granular medium that consists of inelastic frictional particles under microgravity. The main reason that the classical KT fails to model these flows is due to its inability to account for the particle surface friction and its inelastic behavior, which are the two most important factors that need be considered in modeling collisional granular flows. In this study, we have modified the KT model that is able to incorporate these two factors. The inelasticity of a particle is considered by establishing a velocity-dependent expression for the restitution coefficient based on many experimental studies found in the literature, and the particle friction effect is included by using a tangential restitution coefficient that is related to the particle friction coefficient. Theoretical predictions of the free cooling process by the classical KT and the improved KT are compared with the experimental results from a study conducted on an airplane undergoing parabolic flights without the influence of gravity [Y. Grasselli, G. Bossis, and G. Goutallier, Europhys. Lett. 86, 60007 (2009)]. Our results show that both the velocity-dependent restitution coefficient and the particle surface friction are important in predicting the free cooling process of granular flows; the modified KT model that integrates these two factors is able to improve the simulation results and leads to better agreement with the experimental results.
Multiscale Reactive Model for 1,3,5-Triamino-2,4,6-trinitrobenzene Inferred by Reactive MD Simulations and Unsupervised Learning
When high-energy-density materials are subjected to thermal or mechanical insults at extreme conditions (shock loading), a coupled response between the thermo-mechanical and chemical behaviors is systematically induced. Herein we develop a reaction model for the fast chemistry of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) at the mesoscopic scale, where the chemical behavior is determined by underlying microscopic reactive simulations. The slow carbon cluster formation is not discussed in the present work. All-atom reactive molecular dynamics (MD) simulations are performed with the ReaxFF potential, and a reduced-order chemical kinetics model for TATB is fitted to isothermal and adiabatic simulations of single crystal chemical decomposition. Unsupervised machine learning techniques based on non-negative matrix factorization are applied to MD trajectories to model the decomposition kinetics of TATB in terms of a four-component model. The associated heats of reaction are fit to the temperature evolution from adiabatic decomposition trajectories. Using a chemical species analysis, we show that non-negative matrix factorization captures the main chemical decomposition steps of TATB and provides an accurate estimation of their evolution with temperature. The final analytical formulation, coupled to a diffusion term, is incorporated into a continuum formalism, and simulation results are compared one-to-one against MD simulations of 1D reaction propagation along different crystallographic directions and with different initial temperatures. A good agreement is found for both the temporal and spatial evolution of the temperature field.
Evaluating Possible Formation Mechanisms of Criegee Intermediates during the Heterogeneous Autoxidation of Squalene
Organic molecules in the environment oxidatively degrade by a variety of free radical, microbial, and biogeochemical pathways. A significant pathway is heterogeneous autoxidation, in which degradation occurs via a network of carbon and oxygen centered free radicals. Recently, we found evidence for a new heterogeneous autoxidation mechanism of squalene that is initiated by hydroxyl (OH) radical addition to a carbon–carbon double bond and apparently propagated through pathways involving Criegee Intermediates (CI) produced from β-hydroxy peroxy radicals (β-OH-RO 2 •). It remains unclear, however, exactly how CI are formed from β-OH-RO 2 •, which could occur by a unimolecular or bimolecular pathway. Combining kinetic models and multiphase OH oxidation measurements of squalene, we evaluate the kinetic viability of three mechanistic scenarios. Scenario 1 assumes that CI are formed by the unimolecular bond scission of β-OH-RO 2 •, whereas Scenarios 2 and 3 test bimolecular pathways of β-OH-RO 2 • to yield CI. Scenario 1 best replicates the entire experimental data set, which includes effective uptake coefficients vs [OH] as well as the formation kinetics of the major products (i.e., aldehydes and secondary ozonides). Finally, although the unimolecular pathway appears to be kinetically viable, future high-level theory is needed to fully explain the mechanistic relationship between CI and β-OH-RO 2 • in the condensed phase.
Plasma-assisted catalysis for ammonia synthesis in a dielectric barrier discharge reactor: key surface reaction steps and potential causes of low energy yield
Ammonia synthesis experiments were carried out in a coaxial dielectric barrier discharge (DBD) reactor packed with several different supports and metal catalysts. There was a marked increase in the reaction rate, over that obtained in an empty DBD plasma reactor, upon introduction of a packed bed of γ-Al 2 O 3 , Ru/γ-Al 2 O 3 , or SiO 2 particles. The difference in the reaction rates over γ-Al 2 O 3 and Ru/γ-Al 2 O 3 was minimal. Complementary zero-dimensional plasma kinetic model analysis was also performed using inputs from experimental data. This kinetic analysis allowed for gas phase reactions, Eley–Rideal (E–R) reactions, and direct adsorption of radical species on the γ-Al 2 O 3 surface. On the metal surface, dissociative adsorption of N 2 and H 2 , and Langmuir–Hinshelwood reactions were also included. This analysis revealed that, under the conditions of our experiments, ammonia synthesis proceeds principally by the formation of reactive radicals in the gas phase, which then adsorb and participate in E–R reactions on both the metal and support material surfaces. Furthermore, this finding illustrates a challenge for substantially increasing the energy yield for plasma-assisted ammonia synthesis in typical DBD reactors containing packed catalyst beads.
Probing High-Temperature Amine Chemistry: Is the Reaction NH 3 + NH 2 ⇌ N 2 H 3 + H 2 Important?
The reaction NH 3 + NH 2 ⇌ N 2 H 3 + H 2 (R1) has been identified as a key step to explain experimental results for pyrolysis and oxidation of ammonia. However, no direct experimental or theoretical evidence for the reaction has been reported. In the present work, the reaction was studied by ab initio theory and by reinterpretation of experimental data. We could not locate a transition state for R1 occurring as a direct process, but alternative mechanisms yielded an upper bound to k 1 of 1.5 × 10 13 exp(–58.9 kcal mol –1 /RT) cm 3 mol –1 s –1 over 1000–2500 K, several orders of magnitude lower than values applied in modeling. Consistent with the theoretical work, re-evaluation of NH 3 pyrolysis data supported a very low value of k 1 . However, this finding opens up a novel unresolved issue. Current kinetic models cannot capture the NH 3 oxidation behavior in a number of laminar flow reactor and jet-stirred reactor experiments without adopting an improbably high value for k 1 . Furthermore, important oxidation steps might be underestimated or missing from mechanisms.
Observation and Modeling of the Thermal Runaway of High-Capacity Pouch Cells Due to an Internal Short Induced by an Indenter
Owing to the complexity of coupling mechanical and electrical solvers for finite element analysis (FEA) of mechanical abuse of a battery, the simulation should be performed by incorporating a local short circuit model activated based on the status of battery elements. However, the approach should also consider various other conditions of the battery simulated, such as the initial state of charge (SOC), for precise simulations of the internal short. This study proposes an approach developed with a mechanical model and single-particle battery model, along with a reaction kinetics model for thermal abuse using LS-DYNA. Several key parameters were selected, such as the activation criteria, kinetic abuse and element integration points during the internal short circuit induced by the indenter. The impact of these key parameters in the FEA on thermal runaway response for various initial SOCs from 25 to 100 % were analyzed. The FEA results obtained were compared against experimental results with various parameters such as activation criterion of internal short, kinetic abuse based on accelerating rate calorimetry (ARC) data. Finally, the root causes of the discrepancy between the FEA and experimental results are discussed regarding integration point what solver can make difference during calculation.
Kinetic and process modeling of Guerbet coupling chemistry over Cu–Mg–Al mixed oxides
Kinetic modeling of Guerbet coupling chemistry over a CuMgAlO x catalyst is presented. Integration of the model in a process simulation enables assessing a recycling strategy to optimize the production of diesel fuel precursors.
Experimental and Computational Interrogation of Fast SCR Mechanism and Active Sites on H-Form SSZ-13
Experiment and density functional theory (DFT) models are combined to develop a unified, quantitative model of the mechanism and kinetics of fast selective catalytic reduction (SCR) of NO/NO2 mixtures over H-SSZ-13 zeolite. Rates, rate orders, and apparent activation energies collected under differential conditions reveal two distinct kinetic regimes. First-principles thermodynamics simulations are used to determine the relative coverages of free Brønsted sites, chemisorbed NH4+ and physisorbed NH3 as a function of reaction conditions. First-principles metadynamics calculations show that all three sites can contribute to the rate-limiting N-N bond forming step in fast SCR. The results are used to parameterize a kinetic model that encompasses the full range of reaction conditions and recovers observed rate orders and apparent activation energies. Observed kinetic regimes are related to changes in most-abundant surface intermediates. Financial support was provided by the National Science Foundation GAOLI program under award number 1258690-CBET. We thank the Center for Research Computing at Notre