Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Conditional diffusion models”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

JASMINE: a fuel rod thermal-mechanical performance's code

JASMINE, which is developed by China General Nuclear Power Corporation (CGNPC), is a code for calculating thermal-mechanical response of PWR fuel rods. The code models many physical phenomena, including heat conduction through the fuel and cladding to the coolant, cladding elastic and plastic deformation, fuel elastic deformation, fuel swelling and densification,fuel-cladding mechanical interaction, fission gas release from the fuel, rod internal pressure, cladding oxidation and hydriding. Just as most fuel rod codes, JASMINE, which is a quasi-two dimensional code, includes a thermal module, a mechanical module, a fission gas release (FGR) module, and an internal pressure module. For thermal module, the time dependent thermal conduction equation of axisymmetric cylindrical geometry, Halden's fuel thermal conductivity, thermal conductivity integration method and multi-dimension Newton-Raphson procedure are used; for the mechanical module, generalized plane strain hypothesis, cladding-fuel axial lockup model, cladding thermal stress and transfer matrix method are applied; for fission gas release module, the time dependent diffusion equation for a spherical grain, Speight-Turnbull grain surface boundary condition, and Forsberg-Massih's method are used; for the internal pressure module, the ideal gas state equation is used. The code, which is on validation stage, will be used for fuel rod design of nuclear power plants in China in a near future. So far, the preliminary validation process for pellet centerline temperature and fission gas release, which is based on fuel rod test data in FUMEX-III project, has finished. According to the validation results, JASMINE has the ability to reasonably predicts fuel behavior and performance in-pile. JASMINE has good prediction in fuel temperature, and good prediction on FGR as a whole. However, for FGR in the range 1% to 15%, JASMINE over-predicts FGR; for other range, JASMINE underestimates FGR. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Numerical Analysis of Liquid Metal MHD Flow and Heat Transfer for Open-Surface Li Divertor in FNSF

Within the ongoing U.S.-based program on the development of liquid metal plasma-facing components, numerical simulations and analyses are performed to address the feasibility of the open-surface Li divertor. In the previous scoping studies (Smolentsev, 2021), heat-removal capabilities of the divertor were assessed using a simplified flow model for a slug-type velocity profile and constant flow thickness. Here, new analyses take into account forces acting on the flowing Li layer. Three reduced-order mathematical models are applied under the conditions of the U.S. Fusion Nuclear Science Facility (FNSF) to access magnetohydrodynamic (MHD) flow development effects, velocity distribution, and surface waves: 1) fully developed MHD flow; 2) quasi-2-D developing MHD flow; and 3) multiphase MHD flow. The obtained results for MHD flows and the surface heat flux computed with the plasma code scrape-off layer plasma simulation for ITER (SOLPS-ITER) are then used as input data to compute the temperature distribution in the divertor by solving the convection–diffusion energy equation.

Smolentsev, Sergey↗
NASA NTRS1986

Oxidation and embrittlement of Ti-6Al-2Sn-4Zr-2Mo alloy

A thermogravimetric analysis monitoring study has been conducted for Ti-6Al-2Sn-4Zr-2Mo in the 593-760 C range, with a view to its total oxidation kinetics in laboratory air. In addition, tensile elongation was obtained for selected foil specimens after their exposure to simulated Space Shuttle reentry conditions. The total weight gain with time exhibited two parabolic stages separated by a transient region which is the result of a simultaneous increase in the parabolic growth rate constant for the oxide and in oxygen solubility at the oxide-metal interface. A model for the total oxidation kinetics accounting for the two individual components (oxide growth and solid solution formation) is proposed; the activation energy for oxygen diffusion in the alpha-solid solution is shown to approximate the activation energy for the degradation of tensile elongation of the alloy in its foil gage condition.

Shenoy, R. N.↗
NASA NTRS2009

Smoke Point in Co-flow Experiment

The Smoke Point In Co-flow Experiment (SPICE) determines the point at which gas-jet flames (similar to a butane-lighter flame) begin to emit soot (dark carbonaceous particulate formed inside the flame) in microgravity. Studying a soot emitting flame is important in understanding the ability of fires to spread and in control of soot in practical combustion systems space. Previous experiments show that soot dominates the heat emitted from flames in normal gravity and microgravity fires. Control of this heat emission is critical for prevention of the spread of fires on Earth and in space for the design of efficient combustion systems (jet engines and power generation boilers). The onset of soot emission from small gas jet flames (similar to a butane-lighter flame) will be studied to provide a database that can be used to assess the interaction between fuel chemistry and flow conditions on soot formation. These results will be used to support combustion theories and to assess fire behavior in microgravity. The Smoke Point In Co-flow Experiment (SPICE) will lead to a o improved design of practical combustors through improved control of soot formation; o improved understanding of and ability to predict heat release, soot production and emission in microgravity fires; o improved flammability criteria for selection of materials for use in the next generation of spacecraft. The Smoke Point In Co-flow Experiment (SPICE) will continue the study of fundamental phenomena related to understanding the mechanisms controlling the stability and extinction of jet diffusion flames begun with the Laminar Soot Processes (LSP) on STS-94. SPICE will stabilize an enclosed laminar flame in a co-flowing oxidizer, measure the overall flame shape to validate the theoretical and numerical predictions, measure the flame stabilization heights, and measure the temperature field to verify flame structure predictions. SPICE will determine the laminar smoke point properties of non-buoyant jet diffusion flames (i.e., the properties of the largest laminar jet diffusion flames that do not emit soot) for several fuels under different nozzle diameter/co-flow velocity configurations. Luminous flame shape measurements would also be made to verify models of the flame shapes under co-flow conditions. The smoke point is a simple measurement that has been found useful to study the influence of flow and fuel properties on the sooting propensity of flames. This information would help support current understanding of soot processes in laminar flames and by analogy in turbulent flames of practical interest.

Urban, David L.↗
NASA NTRS1978

Molecular evolution of contracting clouds - Basic methods and initial results

The relationship between the dynamics of the interstellar gas and the thermal and chemical effects associated with interstellar molecules and dust is investigated. The evolution of a rather massive isolated initially diffuse cloud under self-gravity is studied, using the equations of hydrodynamics; only radial motions are considered, and the heat, chemical, and radiative-transfer equations are solved simultaneously with the hydrodynamic equations. The relevant chemistry is described along with the thermal model, the radiative-transfer process, and the numerical methods employed. Results for a contracting cloud are discussed in terms of the problem of initial conditions, the dynamical evolution of the cloud, its chemical and thermal evolution, time scales, and column densities. It is shown that the chemical evolution of a massive contracting diffuse cloud is sensitive to such physical properties as temperature and ion abundances, that warm and cool versions of a typical cloud evolve differently, and that the physical origin of this effect is the level of heating due to H2 formation on interstellar dust grains.

Gerola, H.↗
NASA NTRS2016

Investigating Global Ion and Neutral Atom Populations with IBEX and Voyager

The main objective of this project was to investigate pickup ion (PUI) production in the solar wind and heliosheath (the region between the termination shock and the heliopause) and compute the distributed energetic neutral atom fluxes throughout the helioshpere. The simulations were constrained by comparing the model output against observations from Ulysses, New Horizons, Voyager 1 and 2, and IBEX space probes. As evidenced by the number of peer reviewed journal publications resulting from the project (13 plus three submitted) and their citation rate (156 citations over three years), the project has made a lasting contribution to the field. The outcome is a significant improvement of our understanding of the pickup ion production and distribution in the distant heliosphere. The team has accomplished the entire set of tasks A-H set forth in the proposal. Namely, the transport modeling framework has been augmented with two populations of pickup ions (PUIs), the boundary conditions for the plasma and interstellar neutral hydrogen were verified against Ulysses and New Horizons PUI and an optimal set of velocity diffusion parameters established. The multi-component fluxes of PUIs were computed and isotropic velocity distributions generated for each cell in the computer simulation that covered the heliosphere from 1.5 AU to the heliopause. The distributions were carefully compared with in situ measurements at 3 AU (Ulysses), 12 AU (New Horizons), and 80-90 AU (Voyager 1 and 2) as well as those inferred from ENA fluxes measured by Cassini and IBEX (Wu et al., 2016). Some examples of modeldata comparison are shown in Figure 1. We have used coupled MHD-plasma and kinetic-neutral code to investigate the likely range of plasma and magnetic field parameters in the local interstellar medium (LISM), based on the assumption that the shape of the IBEX ribbon could be used to determine the orientation of the interstellar magnetic field. While the magnetic field is believed to be oriented toward the center of the ribbon, constraining its strength requires comparing the model-predicted angular diameter and circularity of the ribbon with the observations. The study, published in Heerikhuisen et al. (2014), found that the most likely range for the LISM magnetic field strength is between 0.2 and 0.3 nT, which is less than previously thought. Figure 2 shows the IBEX data (left) and compares it to the simulation with a 0.2 nT interstellar magnetic field (center) and a 0.4 nT (right).

Florinski, Vladimir↗
DOE OSTI2021

Defect-Driven Oxide Transformations and the Electrochemical Interphase

The redox reaction pathway is crucial to the sustainable production of the fuels and chemicals required for a carbon-neutral society. Our society is becoming increasingly dependent on devices using batteries and electrolyzers, all of which rely on a series of redox reactions. The overall properties of oxide materials make them very well suited for such electrochemical and catalytic applications due to their associated cationic redox properties and the static site-adsorbate interactions. As these technologies have matured, it has become apparent that defect-driven redox reactions, defect-coupled diffusion, and structural transformations that are both time- and rate-dependent are also critical materials processes. This change in focus, considering not only redox properties but also more complex, dynamic behaviors, represents a new research frontier in the molecular sciences as they are strongly linked to device operation and degradation and lie at the heart of various phenomena that take place at electrochemical interfaces. Fundamental studies of the structural, electronic, and chemical transformation mechanisms are key to the advancement of materials and technological innovations that could be implemented in various electrochemical systems. In this Account, we focus on recent studies and advances in characterizing and understanding the dynamic redox evolution and structural transformations that take place in model perovskites and layered oxides under reactive conditions and correlate them with degradation mechanisms and operations in electrolyzers and batteries. We show that the dynamic evolution of oxygen vacancies and cationic migration in the surface or bulk occurs at the solid-liquid interface, using a combination of different synchrotron-based Xray spectroscopies and scattering probes. Detailed redox-structure-reactivity correlation studies show how defects and diffusion processes can be tailored to drive various physical and chemical transformations in electrolyzers and batteries. We also highlight a strong correlation between oxygen redox reactivity and structural reorganization in both model thin films and particles, helping to bridge the gap between fundamental studies of the reaction mechanism and device applications. Finally, on the basis of these findings, we discuss strategies to probe and tune the redox reactivity and structural stability of the redox-active oxide interphase toward devising efficient pathways for energy and chemical harvesting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

AN AB INITIO MODEL FOR COSMIC-RAY MODULATION

A proper understanding of the effects of turbulence on the diffusion and drift of cosmic rays (CRs) is of vital importance for a better understanding of CR modulation in the heliosphere. This study presents an ab initio model for CR modulation, incorporating for the first time the results yielded by a two-component turbulence transport model. This model is solved for solar minimum heliospheric conditions, utilizing boundary values chosen so that model results are in reasonable agreement with spacecraft observations of turbulence quantities in the solar ecliptic plane and along the out-of-ecliptic trajectory of the Ulysses spacecraft. These results are employed as inputs for modeled slab and two-dimensional (2D) turbulence energy spectra. The modeled 2D spectrum is chosen based on physical considerations, with a drop-off at the very lowest wavenumbers. There currently exist no models or observations for the wavenumber where this drop-off occurs, and it is considered to be the only free parameter in this study. The modeled spectra are used as inputs for parallel mean free path expressions based on those derived from quasi-linear theory and perpendicular mean free paths from extended nonlinear guiding center theory. Furthermore, the effects of turbulence on CR drifts are modeled in a self-consistent way, also employing a recently developed model for wavy current sheet drift. The resulting diffusion and drift coefficients are applied to the study of galactic CR protons and antiprotons using a 3D, steady-state CR modulation code, and sample solutions in fair to good agreement with multiple spacecraft observations are presented.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Preliminary Compendium of the Initial Conditions and Evolution of the Fundamental Interactions of SiC with Ag and Pd

Tri-structural isotropic (TRISO) particles are the fuel of choice for very-high temperature reactors. At the core, these spherical particles consist of an inner fuel kernel of UO{sub 2}, UC{sub 2} or a combination of both, which is coated radially outward by successive layers of low density pyrolytic graphite, an inner high density pyrolytic graphite layer, silicon carbide (SiC) and an outer high density pyrolytic graphite layer. SiC is the main diffusion barrier against the release of fission products due to its hardness and high melting point. Irradiation testing of TRISO particles indicates that trace amounts of metallic fission products can damage or potentially escape through the barrier layer. Surrogate experimental studies have previously been performed by various methods seeking to shed light on and explain the diffusion behavior of Ag and Pd. Although some of these experiments have yielded realistic diffusion coefficients the discrepancy of results between different groups is such that the essential details of the diffusive behavior are still to be fully understood. This work aims to understand the fundamental physical and chemical interactions that take place at the interface of SiC and Ag/Pd, and which give rise to the observed diffusion behavior of these metallic species in TRISO particles. Theoretical simulations of the diffusion of Ag through SiC have been exhaustive but typically yield bulk diffusion coefficients that due to the nature of bulk diffusion phenomena (i.e. slow diffusion) the diffusion coefficients are calculated to be orders of magnitude lower than what experimental observations suggest. This in part is due to the difficulty in simulating realistic models that include various polymorphs of SiC, and the dynamical structural transformations that SiC undergoes in the TRISO environment (which are also to be explained). The result is a particularly challenging problem to solve given that the initial conditions of the interactions of Ag and Pd with SiC are difficult to address, both in theoretical models and surrogate experiments. In order to improve these models the approach taken here is to consider fundamental interactions between Ag and SiC that take place in short time scales by varying the initial environmental conditions, i.e. annealing temperature and time, initial amounts of the metallic species (M) Ag, Pd in SiC/M/SiC multilayers. This work aims to understand the fundamental physical and chemical interactions that take place at the interface of SiC and Ag/Pd, and which give rise to the observed diffusion behavior of these metallic species in TRISO particles. In order to do so we have synthesized SiC/Ag/SiC and SiC/Pd/SiC multilayers of various thicknesses by PLD and characterized them using SEM/EDS. Initial results show that upon annealing Ag agglomerates and ruptures the SiC layer to be released. In the case of Pd a strong chemical interaction is deduced from the slow interlayer diffusion and limited release. Further studies using photoelectron spectroscopy and RHEED will be carried out in order obtain detailed information on the chemical and physical transitions that undergo upon annealing of these systems. (authors)

36 MATERIALS SCIENCE↗
NASA NTRS1972

Diffusion models for Jupiter's radiation belt

Solutions are given for the diffusion of trapped particles in a planetary magnetic field in which the first and second adiabatic invariants are preserved but the third is not, using as boundary conditions a fixed density at the outer boundary (the magnetopause) and a zero density at an inner boundary (the planetary surface). Losses to an orbiting natural satellite are included and an approximate evaluation is made of the effects of the synchrotron radiation on the energy of relativistic electrons. Choosing parameters appropriate to Jupiter, the electrons required to produce the observed synchrotron radiation are explained. If a speculative mechanism in which the diffusion is driven by ionospheric wind is the true explanation of the electrons producing the synchrotron emission it can be concluded that Jupiter's inner magnetosphere is occupied by an energetic proton flux that would be a serious hazard to spacecraft.

Jacques, S. A.↗
DOE OSTI2023

A baseline for ensemble-based, time-resolved inflow reconstruction for a single turbine using large-eddy simulations and latent diffusion models

We are interested in reconstructing winds flowing through a turbine on a second-by-second basis over a 10 min window. Previously, we developed a machine learning algorithm that takes in a snapshot of wind speed measurements and generates ensembles of three-dimensional wind field estimates. Here, we use these estimates as initial conditions in large-eddy simulations and reconstruct atmospheric and turbine response dynamic quantities in a synthetic field campaign. In doing so, we establish a baseline for model validation that future time-aware data assimilation techniques will be compared to. In turbine-free case studies, ground truth wind speeds consistently fall within our estimated wind speed distribution for the first 100 s after the simulation start. In simulations with turbines, the wind estimates show a small bias of 0.10 m s 1 and good correlation of 0.80 during the first 100 s. During this window, our estimates of the Blade 1 bending moment and generator power typically span the ground truth, with the estimate of the former performing better overall. In summary, this approach shows promise as a stand-alone technique for reconstructing real-world inflow and turbine dynamics in 1-2 min windows and as a foundation for future time-aware data assimilation techniques.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Analytical Solutions of Transient Drift-Diffusion in P-N Junction Pixel Sensors

Radiation detection in applications ranging from high energy physics to medical imaging rely on solid state detectors, often hybrid pixel detectors with (1) reverse biased p-n junction pixel sensors and (2) readout ASICs, attached by flip chip-bonding. Transient signals characteristics are important in, e.g., matching ASIC and sensor design, modeling and optimizing detector parameters and describing timing and charge sharing properties. Currently analytical forms of transient signals are available for only a few limited cases (e.g., drift or diffusion) or for the steady state (which is not relevant for high energy radiation detection). Tools are available for (relatively slow) numerical evaluation of the transient charge transport. We present here the first analytical solutions of partial differential equations de scribing drift-diffusion-recombination charge transport in planar p-n junction sensors in a variety of conditions: (1) undepleted, (2) fully depleted, (3) taking into account the gradual velocity saturation, and (4) overdepleted. We deduce the Green’s functions which can be applied to any detection problem through simple convolution with the initial conditions. We compare the analytical solutions with Monte Carlo simulations and industry standard simulations (Synopsys Sentaurus), demonstrating good agreement. Using the analytical equations enables fast modeling of the influence of various detector parameters on tracking, imaging and timing performance, describing performance and enabling optimizations for different applications. Finally, we illustrate this model with applications in 3D+T (x,y,z,time) photon tracking and 4D+T (x,y,θ,φ,time) relativistic charged particle tracking.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Phase field-volumetric lattice Boltzmann model of ion uptake in porous nuclear waste form materials under continuous flow

The flow field within the mesopores of sorbent particles plays a crucial role in radionuclide diffusion and ion uptake kinetics, thus, impacting the overall performance of porous nuclear waste form materials. To fundamentally understand the influence of microstructures and material properties on the radionuclide absorption and retention processes requires a coupled multi-physics model that considers the advection and diffusion within the flow field, the reaction at liquid-solid interfaces, and finally, the solid-state diffusion within a complex nanoporous medium. Here, this study employs the volumetric lattice Boltzmann method (VLBM) to accurately and efficiently calculate the steady state velocity field inside the mesopores of sorbent particles. The obtained velocity field is then utilized to calculate the advection of ions in the steady flow. A phase field (PF) model of ion uptake is used to describe the reaction occurring at the solid-liquid interface and diffusion inside the porous medium. The integrated PF-VLBM model is verified in terms of the mass conservation and numerical efficiency and validated qualitatively with experimental observation data. Then, it is applied to study the influence of thermodynamic and kinetic properties, as well as flow field conditions on the ion uptake kinetics. The numerical results demonstrate that the ion uptake kinetics in porous particles has three distinct stages, which is in agreement with the observations in continuous flow experiments. In the first stage, the kinetics is predominantly controlled by the flow field and ion diffusivity in the liquid phase. The kinetics in the second stage is primarily governed by ion diffusivity in the solid phase. In the third stage the system reaches a dynamic equilibrium with a net zero uptake flux at the interface. It is also found that porous structures significantly affect the efficiency and capacity of ion uptake. The simulation results can help to understand the physics behind the observed ion uptake kinetics in experiments and to facilitate the development of constitutive equations that can account for heterogeneous microstructures in engineering performance codes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Hotspots of soil N 2 O emission enhanced through water absorption by plant residue

N 2 O is a highly potent greenhouse gas and arable soils represent its major anthropogenic source. Field-scale assessments and predictions of soil N 2 O emission remain uncertain and imprecise due to the episodic and microscale nature of microbial N 2 O production, most of which occurs within very small discrete soil volumes. Such hotspots of N 2 O production are often associated with decomposing plant residue. Here we quantify physical and hydrological soil characteristics that lead to strikingly accelerated N 2 O emissions in plant residue-induced hotspots. Results reveal a mechanism for microscale N 2 O emissions: water absorption by plant residue that creates unique micro-environmental conditions, markedly different from those of the bulk soil. Moisture levels within plant residue exceeded those of bulk soil by 4–10-fold and led to accelerated N 2 O production via microbial denitrification. The presence of large (Ø >35 μm) pores was a prerequisite for maximized hotspot N 2 O production and for subsequent diffusion to the atmosphere. Understanding and modelling hotspot microscale physical and hydrologic characteristics is a promising route to predict N 2 O emissions and thus to develop effective mitigation strategies and estimate global fluxes in a changing environment.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

Design strategies for self-assembly of discrete targets

Both biological and artificial self-assembly processes can take place by a range of different schemes, from the successive addition of identical building blocks to hierarchical sequences of intermediates, all the way to the fully addressable limit in which each component is unique. In this paper, we introduce an idealized model of cubic particles with patterned faces that allows self-assembly strategies to be compared and tested. We consider a simple octameric target, starting with the minimal requirements for successful self-assembly and comparing the benefits and limitations of more sophisticated hierarchical and addressable schemes. Simulations are performed using a hybrid dynamical Monte Carlo protocol that allows self-assembling clusters to rearrange internally while still providing Stokes-Einstein-like diffusion of aggregates of different sizes. Our simulations explicitly capture the thermodynamic, dynamic, and steric challenges typically faced by self-assembly processes, including competition between multiple partially completed structures. Self-assembly pathways are extracted from the simulation trajectories by a fully extendable scheme for identifying structural fragments, which are then assembled into history diagrams for successfully completed target structures. For the simple target, a one-component assembly scheme is most efficient and robust overall, but hierarchical and addressable strategies can have an advantage under some conditions if high yield is a priority.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

Magnetic storm characteristics of the thermosphere.

Energy and diffusive mass transport associated with the thermospheric circulation are considered in a self-consistent, though mathematically relatively simple, form to describe in a three-dimensional two-constituent model magnetic storm characteristics in composition (N2, O, and He), temperature, and mass-density. It is shown that during disturbed conditions the latitudinal variations of composition and gas temperature reflect the local nature of the magnetic storm heat input assumed to be primarily confined to the auroral zones. Thereby gas temperature and N2 increase, He decreases, and O remains constant through the auroral zones at exospheric heights (due to the superposition of temperature and diffusion effects) in agreement with Ogo 6 mass spectrometer measurements. In contrast, the magnetic storm response in the total mass density is characterized by a strong worldwide component and a relatively insignificant increase toward the poles.

Mayr, H. G.↗
DOE OSTI2015

Two-Dimensional Porous Electrode Model for Capacitive Deionization

Here, ion transport in porous conductive materials is of great importance in a variety of electrochemical systems including batteries and supercapacitors. We here analyze the coupling of flow and charge transport and charge capacitance in capacitive deionization (CDI). In CDI, a pair of porous carbon electrodes is employed to electrostatically retain and remove ionic species from aqueous solutions. We here develop and solve a novel unsteady two-dimensional model for capturing the ion adsorption/desorption dynamics in a flow-between CDI system. We use this model to study the complex, nonlinear coupling between electromigration, diffusion, and advection of ions. We also fabricated a laboratory-scale CDI cell which we use to measure the near-equilibrium, cumulative adsorbed salt, and electric charge as a function of applied external voltage. We use these integral measures to validate and calibrate this model. We further present a detailed computational study of the spatiotemporal adsorption/desorption dynamics under constant voltage and constant flow conditions. We show results for low (20 mM KCl) and relatively high (200 mM KCl) inlet ion concentrations and identify effects of ion starvation on desalination. We show that in both cases electromigrative transport eventually becomes negligible and diffusive ion transport reduces the desalination rate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Kinetic Model for the Reduction of Cu II Sites by NO + NH 3 and Reoxidation of NH 3 -Solvated Cu I Sites by O 2 and NO in Cu-SSZ-13

In this work, a kinetic model is developed for the reduction of Cu II sites by NO + NH 3 and the reoxidation of NH 3 -solvated Cu I sites by O 2 and NO in Cu-SSZ-13. Fourier transform infrared (FTIR) spectroscopy and spatially resolved capillary inlet mass spectrometry (SpaciMS) measurements during transient reactor experiments are utilized to identify the rate parameters associated with NO + NH 3 RHC (reduction half-cycle), proposed to occur via two distinct pathways involving adsorbed NH 3 and gas-phase NH 3 . The resulting NO + NH 3 RHC model is validated using spatiotemporal N 2 measurements covering a wide range of temperatures (200–450 °C) and space velocities (53,000–640,000 h –1 ). N 2 O formation is observed and modeled during NO + NH 3 RHC, with quantitative validation under standard selective catalytic reduction (SCR) conditions. Experimentally measured enthalpic and entropic changes associated with O 2 adsorption on NH 3 -solvated Cu I (ZCu(NH 3 ) 2 ) complexes [ Kamasamudram, K. Catal. Today 2010 , 151 (3–4), 212-222], along with activation energies estimated computationally for the intercage diffusion of ZCu(NH 3 ) 2 complexes [ Paolucci, C. Science 2017 , 357 (6 354), 898-903], are incorporated into a mean field kinetic model for the low-temperature oxidation half-cycle (OHC). Significant NH 3 release is observed during the isothermal oxidation of Cu I sites, attributed to desorption of NH 3 ligands from NH 3 -solvated Cu II dimers (Z 2 Cu 2 (NH 3 ) 4 O 2 ). Reduction of these dimeric complexes leads to the consumption of one NO/Cu II , contradicting the expected reduction stoichiometry. Inclusion of a global Arrhenius rate for the NO titration of Z 2 Cu 2 (NH 3 ) 4 O 2 complexes provides accurate representations of standard SCR on reduced and oxidized catalysts, predicting transient NO and NH 3 consumption between 150 and 250 °C as a function of hydrothermal aging. Deactivation of low-temperature standard SCR by NH 3 is observed at high NH 3 pressures, modeled via the formation of superoxo amino (ZCu(NH 3 ) 3 OO*) complexes during NH 3 titration of Z 2 Cu 2 (NH 3 ) 4 O 2 complexes [ Negri, C. J. Am. Chem. Soc. 2020 , 142 (37), 15884-15896]. The redox kinetic model presented here provides a foundational description of active site redox during low-temperature standard SCR, combining the recent kinetic, spectroscopic, and computational findings on the mechanism of standard SCR over Cu-SSZ-13.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗