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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Influence of Inorganic Carbon Sources on Low-pH Succinic Acid Production by Issatchenkia orientalis : Process Insights and Kinetic Analysis

Bio-based succinic acid (SA) production has attracted significant interest; however, the relationship between fermentation conditions and SA biosynthesis remains insufficiently understood, particularly under low-pH operation. In this study, an engineered, acid-tolerant, nonmodel yeast, Issatchenkia orientalis , was employed to investigate the role of inorganic carbon supplementation in SA production from glucose. Because regulation of gas-phase CO 2 during fermentation is challenging due to low solubility and off-gas losses, liquid-phase inorganic carbon sources, carbonic acid (H 2 CO 3 ) and sodium carbonate (Na 2 CO 3 ), were evaluated as indirect CO 2 donors. Fermentations were conducted in a corn steep liquor-based medium under acidic conditions. Shake-flask experiments demonstrated that H 2 CO 3 supplementation increased SA production, achieving a maximum titer of 8.9 g/L and a yield of 0.46 g/g glucose. Kinetic analysis of bench-scale fermentations showed that the SA formation was well described by the Luedeking–Piret model, indicating mixed growth-associated product formation with a substantial nongrowth-associated contribution under carbonic acid supplementation. Guided by these kinetic insights, a two-stage fed-batch fermentation strategy was implemented, resulting in an SA titer of 30 g/L and a yield of 0.57 g/g glucose within 115 h. Overall, this work provides process-relevant insights into integrating inorganic carbon utilization with low-pH fermentation to inform more sustainable SA biomanufacturing.

fed-batch fermentation↗
DOE OSTI2024

Node Distortions in UiO-66 Inform Negative Thermal Expansion Mechanisms: Kinetic Effects, Frustration, and Lattice Hysteresis

In metal–organic frameworks (MOFs) the interplay between the dynamics of individual components and how these are constrained by the extended lattice can yield unusual emergent phenomena. For the archetypal Zr-MOF, UiO-66, we explore the cooperative dynamics of a Zr-node transformation that gives rise to negative thermal expansion (NTE). Here, using in situ synchrotron X-ray scattering, with powder diffraction and pair distribution function (PDF) analyses, we identify lattice hysteresis and a thermal ramp-rate-dependence of the thermal expansion. Specifically, kinetic trapping of distorted node states formed at high temperature, leads to broad variability in the apparent thermal expansion which ranges from large positive to large negative thermal expansion with coefficients of thermal expansion (CTE) from +45 to –80 × 10 –6 K –1 . Time-resolved relaxation studies at selected temperatures suggest that when equilibrated UiO-66 is intrinsically NTE, with a CTE of –35 × 10 –6 K –1 . Kinetic trapping of the node-distorted state following high temperature activation has broad implications for characterization and applications of these Zr-MOFs; the nonequilibrium node state depends on the thermal history of the sample with quench vs slow cooling likely to impact gas binding, pore volume, and accessible catalytic sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Fast microflow kinetics and acid catalyst deactivation in glucose conversion to 5-hydroxymethylfurfural

5-Hydroxymethyl furfural (HMF) is an important platform chemical because it can be upgraded to various drop-in and performance-advantaged products. The cascade reaction of HMF production from glucose over a Lewis acid (CrCl 3 ) and a Brønsted acid (HCl) catalyst in aqueous media is investigated in a microreactor at short residence times and high temperatures. We study the formation of various chromium species using UV-visible spectrophotometry and elucidate the Cr(III) speciation. The catalyst reactivity increases sharply at short residence times, and then drops at long times. This indicates that the catalyst treatment plays a vital role in getting optimal reactivity, and recording the catalyst history is necessary. We develop a kinetic model to describe the catalyst speciation as well as the Lewis and Brønsted acid-catalyzed reaction kinetics using a hierarchical approach. Here, the model is in good agreement with experiments. We demonstrate the benefits of tandem Lewis-external added Brønsted acid catalysis in processing time, productivity, and catalyst stability. We apply this model to optimize the HMF yield and obtain ~36% yield at 200 °C in 7 min and report the highest productivity of ~15% yield per min, demonstrating the opportunity of reaching high productivity at short residence times.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Kinetics of furfural electrochemical hydrogenation and hydrogenolysis in acidic media on copper

Electrochemical processes can be implemented for the valorization of biomass-derived species such as furfural to generate fine chemicals and fuels. The electrochemical hydrogenation and hydrogenolysis (ECH) of furfural (FF) can produce furfuryl alcohol (FA) and 2-methylfuran (MF) as the major products over Cu catalysts in acidic conditions. The production of these species are in competition and the kinetics of these reactions should be studied so that the product distribution can be better controlled. In this work, the competing kinetics of furfural ECH to furfuryl alcohol and 2-methylfuran were studied on Cu in acidic media by using the applied cathodic potential, temperature, and initial concentration of furfural as probes. Furthermore, an increased temperature of the system was shown to promote the MF production in the range tested (15 °C and 45 °C), however the production of FA was decreased when the temperature was increased from 35 °C to 45 °C, due to significant promotion of side reactions. By varying the concentration of FF used in bulk electrolysis, we saw that the rates of reaction to FA and MF shift from positive order to zero order, suggesting a Langmuir–Hinshelwood or Eley–Rideal mechanism at –0.56 V vs. RHE and 25 °C. An analysis of the reaction mechanisms showed that a non-competitive Langmuir–Hinshelwood mechanism is likely occurring. In addition, we suggest the likely rate limiting steps based on the mechanisms are the first hydrogenation step of FF to C 4 H 3 O–CH 2 O to form FA, and the C–O cleavage of the C 4 H 3 O–CHOH intermediate to form MF.

09 BIOMASS FUELS↗
DOE OSTI2022

Radiation-induced reaction kinetics of Zn 2+ with e S - and Cl 2 ˙ - in Molten LiCl–KCl eutectic at 400–600 °C

We report molten chloride salts are currently under consideration as combined coolant and liquid fuel for next-generation molten salt nuclear reactors. Unlike complementary light-water reactor technologies, the radiation science underpinning molten salts is in its infancy, and thus requires a fundamental mechanistic investigation to elucidate the radiation-driven chemistry within molten salt reactors. Here we present an electron pulse radiolysis kinetics study into the behaviour of the primary radiolytic species generated in molten chloride systems, i.e., the solvated electron (e S - ) and di-chlorine radical anion (Cl 2 ˙- ). We examine the reaction of e S - with Zn 2+ from 400–600 °C (E a = 30.31 ± 0.09 kJ mol -1 ), and the kinetics and decay mechanisms of Cl 2 ˙- in molten lithium chloride-potassium chloride (LiCl–KCl) eutectic. In the absence of Zn 2+ , the lifetime of e S - was found to be dictated by residual impurities in ostensibly “pure” salts, and thus the observed decay is dependent on sample history rather than being an intrinsic property of the salt. The decay of Cl 2 ˙- is complex, owing to the competition of Cl 2 ˙- disproportionation with several other chemical pathways, one of which involves reduction by radiolytically-produced Zn + species. Overall, the reported findings demonstrate the richness and complexity of chemistry involving the interactions of ionizing radiation with molten salts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Reaction mechanism and kinetics for N 2 reduction to ammonia on the Fe–Ru based dual-atom catalyst

Environmental and energy considerations demand that the Haber-Bosch process for reducing N 2 to NH 3 be replaced with electrochemical ammonia synthesis where the H atoms come from water instead of from H 2 . But a practical realization of electrochemical N 2 reduction reaction (NRR) requires the development of new generation electrocatalysts with low overpotential and high Faraday efficiency (FE). A major problem here is that the hydrogen evolution reaction (HER) competes with NRR. Herein, we consider new generation dual-site catalysts involving two different metals incorporated into a novel two-dimensional C 3 N–C 2 N heterostructure that provides a high concentration of well-defined but isolated active sites that bind two distinct metal atoms in a framework that facilitates electron transfer. We report here the mechanism and predicted kinetics as a function of applied potential for both NRR and HER for the (Fe–Ru)/C 3 N–C 2 N dual atom catalyst. These calculations employ the grand canonical potential kinetics (GCP-K) methodology to predict reaction free energies and reaction barriers as a function of applied potential. The rates are then used in a microkinetic model to predict the turn-over-frequencies (TOF) as a function of applied potential. At U = 0 V, the FE for NRR is 93%, but the current is only 2.0 mA cm –2 . The onset potential (at 10 mA cm –2 ) for ammonia on Fe–Ru/C 3 N–C 2 N is –0.22 V RHE . This leads to a calculated TOF of 434 h –1 per Fe–Ru site. In conclusion, we expect that the mechanisms for NRR and HER developed here will help lead to new generations of NRR with high TOF and FE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Preservation of kinetics parameters generated by Monte Carlo calculations in two-step deterministic calculations

The generation of accurate kinetic parameters such as mean generation time Λ and effective delayed neutron fraction β eff via Monte Carlo codes is established. Employing these in downstream deterministic codes warrants another step to ensure no additional error is introduced by the low-order transport operator when computing forward and adjoint fluxes for bilinear weighting of these parameters. Another complexity stems from applying superhomogenization (SPH) equivalence in non-fundamental mode approximations, where reference and low-order calculations rely on a 3D full core model. In these cases, SPH factors can optionally be computed for only part of the geometry while preserving reaction rates and K-effective, but the impact of such approximations on kinetics parameters has not been thoroughly studied. This paper aims at studying the preservation of bilinearly-weighted quantities in the Serpent–Griffin calculation procedure. Diffusion and transport evaluations of IPEN/MB-01, Godiva, and Flattop were carried out with the Griffin reactor physics code, testing available modeling options using Serpent-generated multigroup cross sections and equivalence data. Verifying Griffin against Serpent indicates sensitivities to multigroup energy grid selection and regional application of SPH equivalence, introducing significant errors; these were demonstrated to be reduced through the use of a transport method together with a finer energy grid.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2021

Wave-kinetic approach to zonal-flow dynamics: Recent advances

The basic physics of drift-wave turbulence and zonal flows has long been studied within the framework of the wave-kinetic theory. Recently, this framework has been reexamined from first principles, which has led to more accurate yet still tractable “improved” wave-kinetic equations. In particular, these equations reveal an important effect of the zonal-flow “curvature” (the second radial derivative of the flow velocity) on the dynamics and stability of drift waves and zonal flows. Here, we overview these recent findings and present a consolidated high-level picture of (mostly quasilinear) zonal-flow physics within reduced models of drift-wave turbulence.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Probabilistic effects of porosity and chemical kinetics on the shock initiation of an octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) based explosive

In this work, we investigate the effects of porosity and chemical reactivity on the shock initiation of an HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine)-based polymer bonded explosive due to thin flyer impact using two-dimensional mesoscale simulations. Microstructural samples are computationally generated, and the calculated shock response is compared to experiments. The sample dimensions are 0.1×1.05 mm 2 , and each sample accounts for grain scale heterogeneities, including randomized grain morphology and pore spacing. Simulations are performed using the Lawrence Livermore National Laboratory (LLNL) arbitrary Lagrangian–Eulerian multi-physics code ALE3D. Chemistry and equation of states are handled with LLNL's thermochemical code Cheetah. We employ a modified Arrhenius-based chemical kinetics model that scales the temperature exponent fitting parameter with flyer shock conditions. This new model is calibrated to the mean response of experimental shock initiation thresholds for three separate Kapton flyer thicknesses. A simplified shock initiation criterion is proposed, which classifies the macroscale initiation response based on cross-sectional temperature profiles of the shocked sample. This criterion is used to further investigate the probabilistic response of the sample to variations in the mean porosity and chemical kinetics rate, and we find an inverse correlation between the shock pressure and the confidence interval of the experimental threshold velocity. Furthermore, the methodology presented in this work for quantifying the probabilistic nature of shock initiation is material agnostic. These mesoscale studies may be used to inform continuum scale models and expedite the development of future, tailored energetic formulations.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Adaptive tau-leaping methods for microscopic-lattice kinetic Monte Carlo simulations

Traditional Kinetic Monte Carlo (KMC) approaches, rooted in Gillespie’s stochastic simulation algorithm, become computationally demanding in systems with a large range of timescales. The goal of this work is to propose and study new adaptive lattice-KMC time integration strategies for spatially non-uniform systems. To that end, two novel adaptive tau-leaping methods and their corresponding time integration strategies are developed based on the idea of the “n-fold” direct KMC method. These strategies allow for the simultaneous execution of multiple reactions, advancing time by adaptively selected coarse increments. We present numerical experiments comparing the proposed methods with existing approaches in a catalytic surface kinetics application involving ammonia decomposition.

Bimolecular reactions↗
DOE OSTI2024

Kinetic corrections to heat-flow and Nernst advection for laser heated plasmas

Reduced models for approximating the impact of kinetic electron behavior on the transport of thermal energy and magnetic field are investigated. The thermal flux limiter has improved agreement with Vlasov–Fokker–Planck data when a harmonic form is used that adjusts the electron mean free path to account for electron–electron collisions; these results apply to both unmagnetized and magnetized plasmas. Once a magnetic field is incorporated, the mean free path should also be modified using the electron gyroradius. A flux limiter on Nernst advection of magnetic fields is also required; a form that limits Nernst by the same fraction as the thermal heat-flow best reproduces kinetic simulations. A flux limiter form for the cross terms (Righi–Leduc and cross-gradient-Nernst) is also suggested. Hohlraum simulations relevant to fusion experiments on the National Ignition Facility are found to be sensitive to all of these details.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Plasma hydrodynamics from mean force kinetic theory

Mean force kinetic theory is used to evaluate the electrical conductivity, thermal conductivity, electrothermal coefficient, thermoelectric coefficient, and shear viscosity of a two-component plasma. The results are compared with molecular dynamics simulations. These simulations are made possible by assuming a repulsive Coulomb force for all interactions. Good agreement is found for all coefficients up to a Coulomb coupling strength of Γ ≈ 20. This is over 100-times larger than the coupling strength at which traditional theories break down. It is concluded that mean force kinetic theory is a promising framework for extending hydrodynamics to dense plasmas.

Electrical conductivity↗
DOE OSTI2020

Kinetics of the luminescence decay of Fe{sup 2+} impurity centres in polycrystalline ZnSe upon excitation by an electron beam

The kinetics of the decay of the luminescence of Fe{sup 2+} ions is measured at nitrogen temperature in polycrystalline ZnSe excited by a short pulse of accelerated electrons. The time dependence of the luminescence intensity differs from the exponential one, observed upon excitation of luminescence by a short light pulse. The obtained nonexponential dependence is theoretically described. The explanation is based on the quenching effect of the excited state of the Fe{sup 2+} ion by free electrons of the volume charge of the current of accelerated electrons in the sample (Auger effect). It was shown that the relaxation of the volume charge after the electron-accelerating voltage is removed makes a significant contribution to the decay kinetics of the impurity luminescence. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Kinetic description of site ensembles on catalytic surfaces

Significance The kinetic assessment of catalytic reactions is essential to the design and application of thermochemical processes useful in petrochemical synthesis, energy conversion, and environmental remediation. We demonstrate that the ubiquitously used Langmuir–Hinshelwood formalism is incomplete and fails to correctly describe even simple catalytic reactions (e.g., A + A → A 2 ). An accurate kinetic description requires explicit rate equations for multisite configurations (e.g., A*–A* pairs) to account for the nonrandom clustering/isolation of surface species. We rigorously describe clustering/isolation phenomena by derivation of coverage-dependent stoichiometric coefficients, which capture the distinct influence each elementary step exerts on each catalytic site ensemble—thereby overcoming limitations of the mean-field (i.e., Hinshelwood) assumption in describing reactions of mobile Langmuirian adsorbates on catalytic surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Electron heating in kinetic-Alfvén-wave turbulence

We report analytical and numerical investigations of subion-scale turbulence in low-beta plasmas using a rigorous reduced kinetic model. We show that efficient electron heating occurs and is primarily due to Landau damping of kinetic Alfvén waves, as opposed to Ohmic dissipation. This collisionless damping is facilitated by the local weakening of advective nonlinearities and the ensuing unimpeded phase mixing near intermittent current sheets, where free energy concentrates. The linearly damped energy of electromagnetic fluctuations at each scale explains the steepening of their energy spectrum with respect to a fluid model where such damping is excluded (i.e., a model that imposes an isothermal electron closure). In conclusion, the use of a Hermite polynomial representation to express the velocity-space dependence of the electron distribution function enables us to obtain an analytical, lowest-order solution for the Hermite moments of the distribution, which is borne out by numerical simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

On-lattice kinetic Monte Carlo approaches for modeling molecular anisotropy in resveratrol crystallization

Stilbenes are a class of organic compounds with broad-ranging pharmaceutical and agricultural applications, which are typically isolated and purified through recrystallization. We are motivated by reducing experimental waste and optimizing yield via developing predictive simulations for processing-dependent crystal morphologies. Using resveratrol as a model stilbene system, we have developed an approach for simulating crystallization with molecular resolution using on-lattice kinetic Monte Carlo. In this work, we highlight modifications to the Stochastic Parallel PARticle Kinetic Simulator (SPPARKS) software package, which were essential to this application. Key enhancements include the incorporation of non-orthogonal cell shapes and monomer anisotropy approximations using bound hard spheres. This new SPPARKS application has been applied to resveratrol with attachment energy libraries obtained from density functional theory, resulting in excellent agreement with experimental morphology prediction.

crystallization↗
DOE OSTI2022

Kinetic theory of particle-in-cell simulation plasma and the ensemble averaging technique

Abstract We derive the kinetic theory of fluctuations in physically and numerically stable particle-in-cell (PIC) simulations of electrostatic plasmas. The starting point is the single-time correlation at the start of the simulation between the statistical fluctuations of the weighted densities of macroparticle centers in the plasma particle phase-space. The fluctuations are associated with different initial conditions, typically due to the random initial conditions (in velocity space) of the macroparticles/simulation plasma, assigned according to their initial distribution of probability. The single-time correlations at all time steps and in each spatial grid cell are then determined from the Laplace–Fourier transforms of the discretized Klimontovich-like equation for the macroparticles and Maxwell’s equations for the fields, as computed by modern PIC codes. We recover the expressions for the electrostatic field and the plasma particle density fluctuation autocorrelation spectra as well as the kinetic equations describing the average evolution of PIC-simulated plasma particles, first derived by Langdon (1970b Proc. 4th Conf. Numerical Simulation of Plasmas ) using a test macroparticle approach perturbing a discretized Vlasovian plasma and then averaging the obtained physical quantity over the initial macroparticle velocity distribution. We generalize and extend these results to the modern algorithms in PIC codes using arbitrary macroparticle weights. Analytical estimates of statistical fluctuation amplitudes are derived as a function of the plasma simulation parameters, using the central limit theorem in the limit of a large number of macroparticles per cell. The theory is then used to analyze the ensemble averaging technique of PIC simulations where statistical averages are performed over ensembles of PIC simulations, modeling the same plasma physics problem but using different statistical realizations of the initial distribution functions of the macroparticles. This method is illustrated by linear Landau damping uncovering (from noise, which is usually considered numerical) the physical fluctuations driven by a single small amplitude electrostatic wave perturbing a PIC simulation plasma in equilibrium.

fluctuations correlations↗
DOE OSTI2026

Drift-kinetic effects of tungsten on plasma response to RMP in ITER

Here, effects of high- Z ( Z is the particle charge number) tungsten impurity ions on the plasma response to the resonant magnetic perturbation (RMP) field are numerically investigated for the ITER 15 MA baseline scenario, where the tungsten contribution to the plasma response is computed with a drift-kinetic model while the bulk thermal particle contributions follow the fluid approximation. The study yields three highlights: (i) the drift-kinetic contribution of the tungsten impurity exerts minor influence on the plasma response compared to that computed by the pure fluid model without tungsten; (ii) a new figure of merit, based on the resonant spectrum perturbation at the plasma boundary surface, results in different optimal coil phasing compared to that previously obtained by maximizing the edge-peeling plasma response; (iii) the optimal $n = 3$ RMP (for edge localized mode (ELM) control, $n$ is the toroidal mode number) is found to induce a large tungsten particle influx near the plasma edge associated with the neoclassical toroidal viscosity. The study thus provides useful data on the compatibility of the full tungsten wall with RMP ELM control in ITER.

ITER↗