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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.

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At least 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

ECAR-7932 Rev 0 Large Eddy Simulation of MARVEL Reactor Core Subchannel to Evaluate Model Uncertainty of Reynolds-Averaged Navier-Stokes Equation Based Computational Fluid Dynamics Analysis

In the previous work (ECAR-7210), the peak cladding temperature of the MARVEL microreactor has been evaluated by steady-state Reynolds-Averaged Navier-Stokes (RANS) based computational fluid dynamics (CFD) simulations. Although numerical uncertainties of RANS-based CFD simulations has been assessed in ECAR-7210, the model uncertainty of RANS turbulence models must be investigated to resolve the issues related to inaccurate prediction of turbulent heat flux and flow pulsation in a tight lattice rod bundle using the steady-state RANS simulations. Consequently, this ECAR conducted a high-fidelity CFD analysis utilizing Large Eddy Simulation (LES) to generate reference data and investigated the model uncertainty of RANS-based CFD simulations.

21 - SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLAN↗
DOE OSTI2020

Exciton Delocalization in Indolenine Squaraine Aggregates Templated by DNA Holliday Junction Scaffolds

Exciton delocalization plays a prominent role in the photophysics of molecular aggregates, ultimately governing their particular function or application. DNA is a compelling scaffold in which to template molecular aggregates and promote exciton delocalization. As individual dye molecules are the basis of exciton delocalization in molecular aggregates, their judicious selection is important. Motivated by their excellent photostability and spectral properties, here we examine the ability of squaraine dyes to undergo exciton delocalization when aggregated via a DNA Holliday junction (HJ) template. A commercially available indolenine squaraine dye was chosen for the study given its strong structural resemblance to Cy5, a commercially available cyanine dye previously shown to undergo exciton delocalization in DNA HJs. Three types of DNA-dye aggregate configurations—transverse dimer, adjacent dimer, and tetramer—were investigated. Signatures of exciton delocalization were observed in all squaraine-DNA aggregates. Specifically, strong blue shift and Davydov splitting were observed in steady-state absorption spectroscopy and exciton-induced features were evident in circular dichroism spectroscopy. Strongly suppressed fluorescence emission provided additional, indirect evidence for exciton delocalization in the DNA-templated squaraine dye aggregates. To quantitatively evaluate and directly compare the excitonic Coulombic coupling responsible for exciton delocalization, the strength of excitonic hopping interactions between the dyes were obtained by simultaneous fitting the experimental steady-state absorption and CD spectra via a Holstein-like Hamiltonian in which, following the theoretical approach of Kühn, Renger, and May, the dominant vibrational mode is explicitly considered. The excitonic hopping strength within indolenine squaraines was found to be comparable to that of the analogous Cy5 DNA-templated aggregate. The squaraine aggregates adopted primarily an H-type (dyes oriented parallel to each other) spatial arrangement. Extracted geometric details of dye mutual orientation in the aggregates enabled close comparison of aggregate configurations and the elucidation of the influence of dye angular relationship on excitonic hopping interactions in squaraine aggregates. Furthermore, these results encourage the application of squaraine-based aggregates in next generation systems driven by molecular excitons.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Dynamics of nonequilibrium magnons in gapped Heisenberg antiferromagnets

Nonequilibrium dynamics in spin systems is a topic currently under intense investigation as it provides fundamental insights into thermalization, universality, and exotic transport phenomena. While most of the studies have been focused on ideal closed quantum many-body systems such as ultracold atomic quantum gases and one-dimensional spin chains, driven-dissipative Bose gases in steady states away from equilibrium in classical systems also lead to intriguing nonequilibrium physics. Here, in this work, we theoretically investigate out-of-equilibrium dynamics of magnons in a gapped Heisenberg quantum antiferromagnet based on Boltzmann transport theory. We show that, by treating scattering terms beyond the relaxation-time approximation in the Boltzmann transport equation, energy and particle number conservation mandate that nonequilibrium magnons cannot relax to equilibrium, but decay to other nonequilibrium stationary states. The only decay channel for these stationary states back to equilibrium is through the nonconserving interactions (i.e., changing particle number and/or energy within the magnon system) such as boundary or magnon-phonon scattering. At low temperatures, these nonconserving interactions are much slower processes than intrinsic magnon-magnon interaction in a gapped spin system. Using magnon-phonon interaction as a quintessential type of nonconserving interaction, we then propose that nonequilibrium steady states of magnons can be maintained and tailored using periodic driving at frequencies faster than relaxation due to phonon interactions. These findings reveal a class of classical material systems that are suitable platforms to study nonequilibrium statistical physics and macroscopic phenomena such as classical Bose-Einstein condensation of quasiparticles and magnon supercurrents that are relevant for spintronic applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Investigating bubble pressures in irradiated UO 2 for understanding fragmentation of high burnup structure

This report summarized work carried out to investigate mechanisms relevant to fragmentation of high burnup UO 2 fuel. High pressure bubbles that form in high burnup structure are thought to be responsible for fragmentation and pulverization, when exposed to a temperature ramp during a transient. The over-pressurization of the bubbles during normal operation is a pre-requisite for this mechanism to occur. Therefore, in this work we investigate the role of interstitials, produced through irradiation, in over-pressurizing the bubbles by using a combined molecular dynamics (MD) and cluster dynamics approach. Firstly, the energies for the annihilation of interstitials and vacancies at bubbles have been determined from MD as a function of bubble pressure. Secondly, these reaction energies have been implemented in the cluster dynamics code Centipede to determine the steady-state defect concentrations and bubble pressure under irradiation. It was found that there is a transition from low pressure bubbles, at high temperature, to high pressure bubbles, at low temperatures. This indicates the formation of over-pressurized bubbles in the low temperature periphery of the pellet, where high burnup structure forms. This result supports the hypothesis that over-pressurized bubbles form during steady-state operation and can then contribute to fragmentation during a transient. Future work will examine the influence of bubble pressure on Xe diffusion and study the impact of other sinks (e.g. grain boundaries and dislocations) that are relevant to high burnup structure. Ultimately, the goal is to provide predictions of the bubble pressure as a function of burnup that can be used to derive a more mechanistic fragmentation threshold for use in BISON.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Expanding-box Quasilinear Model of the Solar Wind

The expanding-box model of the solar wind has been adopted in the literature within the context of magnetohydrodynamics, hybrid, and full particle-in-cell simulations to investigate the dynamic evolution of the solar wind. The present paper extends such a method to the framework of self-consistent quasilinear kinetic theory. It is shown that the expanding-box quasilinear methodology is largely equivalent to the inhomogeneous steady-state quasilinear model discussed earlier in the literature, but a distinction regarding the description of wave dynamics between the two approaches is also found. The expanding-box quasilinear formalism is further extended to include the effects of a spiraling solar-wind magnetic field as well as collisional age effects. The present finding shows that the expanding-box quasilinear approach and the steady-state global-kinetic models may be employed interchangeably in order to address other more complex problems associated with the solar-wind dynamics.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Structure and Site Evolution of Framework Ni Species in MIL-127 MOFs for Propylene Oligomerization Catalysis

A mixed-valence oxotrimer metal–organic framework (MOF), Ni-MIL-127, with a fully coordinated nickel atom and two iron atoms in the inorganic node, generates a missing linker defect upon thermal treatment in helium (>473 K) to engender an open coordination site on nickel which catalyzes propylene oligomerization devoid of any cocatalysts or initiators. This catalyst is stable for ~20 h on stream at 500 kPa and 473 K, unprecedented for this chemistry. The number of missing linkers on synthesized and activated Ni-MIL-127 MOFs is quantified using temperature-programmed oxidation, 1 H nuclear magnetic resonance spectroscopy, and X-ray absorption spectroscopy to be ~0.7 missing linkers per nickel; thus, a majority of Ni species in the MOF framework catalyze propylene oligomerization. In situ NO titrations under reaction conditions enumerate ~62% of the nickel atoms as catalytically relevant to validate the defect density upon thermal treatment. Propylene oligomerization rates on Ni-MIL-127 measured at steady state have activation energies of 55–67 kJ mol –1 from 448 to 493 K and are first-order in propylene pressures from 5 to 550 kPa. Density functional theory calculations on cluster models of Ni-MIL-127 are employed to validate the plausibility of the missing linker defect and the Cossee–Arlman mechanism for propylene oligomerization through comparisons between apparent activation energies from steady-state kinetics and computation. Here this study illustrates how MOF precatalysts engender defective Ni species which exhibit reactivity and stability characteristics that are distinct and can be engineered to improve catalytic activity for olefin oligomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Coupled Neutronics - Thermal-Hydraulics - Thermomechanics modeling of Molten Chloride Reactor

Molten Salt Reactors (MSRs) are innovative Generation-IV nuclear reactors known for their enhanced safety features, fuel economy, and fuel cycle advancements. However, designing and studying these reactors present unique safety and modeling challenges. The Department of Energy (DOE)'s Nuclear Energy Advanced Modeling and Simulation program addresses these challenges through the development of flexible multi-fidelity, multiphysics simulation tools. This study exemplifies NEAMS tools' capabilities by modeling a chloride-based micro-MSR: Griffin for neutronics simulations, Pronghorn for thermal-hydraulics simulations, and BISON for thermomechanics simulations. These tools are integrated into a comprehensive 3D multiphysics model, successfully capturing steady-state and transient reactor operations. A loss of flow accident is examined as an illustrative example of transient behavior. Additionally, this paper contributes to demonstrating the theoretical feasibility of micro-MSR concepts, which have received less attention compared to other designs. The subsequent sections provide a brief description of the MSR concept studied, an overview of the computational tools used, and present results for both steady-state operation and a loss of flow accident.

42 - ENGINEERING↗
DOE OSTI2023

Mapping the influence of ligand electronics on the spectroscopic and 1 O 2 sensitization characteristics of Pd( ii ) biladiene complexes bearing phenyl–alkynyl groups at the 2- and 18-positions

Photodynamic therapy (PDT) is a promising treatment for certain cancers that proceeds via sensitization of ground state 3 O 2 to generate reactive 1 O 2 . Classic macrocyclic tetrapyrrole ligand scaffolds, such as porphyrins and phthalocyanines, have been studied in detail for their 1 O 2 photosensitization capabilities. Despite their compelling photophysics, these systems have been limited in PDT applications because of adverse biological side effects. Conversely, the development of non-traditional oligotetrapyrrole ligands metalated with palladium (Pd[DMBil1]) have established new candidates for PDT that display excellent biocompatibility. Herein, the synthesis, electrochemical, and photophysical characterization of a new family of 2,18-bis(phenylalkynyl)-substituted Pd II 10,10-dimethyl-5,15-bis(pentafluorophenyl)-biladiene (Pd[DMBil2-R]) complexes is presented. These second generation biladienes feature extended conjugation relative to previously characterized Pd II biladiene scaffolds (Pd[DMBil1]). We show that these new derivatives can be prepared in good yield and, that the electronic nature of the phenylalkynyl appendages dramatically influence the Pd II biladiene photophysics. Extending the conjugation of the Pd[DMBil1] core through installation of phenylacetylene resulted in a ~75 nm red-shift of the biladiene absorption spectrum into the phototherapeutic window (600–900 nm), while maintaining the Pd II biladiene's steady-state spectroscopic 1 O 2 sensitization characteristics. Varying the electronics of the phenylalkyne groups via installation of electron donating or withdrawing groups dramatically influences the steady-state spectroscopic and photophysical properties of the resulting Pd[DMBil2-R] family of complexes. The most electron rich variants (Pd[DMBil2-N(CH3)2]) can absorb light as far red as ~700 nm but suffer from significantly reduced ability to sensitize formation of 1 O 2 . By contrast, Pd[DMBil2-R] derivatives bearing electron withdrawing functionalities (Pd[DMBil2-CN] and Pd[DMBil2-CF3]) display 1 O 2 quantum yields above 90%. The collection of results we report suggest that excited state charge transfer from more electron-rich phenyl-alkyne appendages to the electron deficient biladiene core circumvents triplet sensitization. The spectral and redox properties, as well as the triplet sensitization efficiency of each Pd[DMBil2-R] derivative is considered in relation to the Hammett value (σp) for each biladiene's R-group. More broadly, the results reported in this study clearly demonstrate that biladiene redox properties, spectral properties, and photophysics can be perturbed greatly by relatively minor alterations to biladiene structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Liquid metal walls

Here, the plasma performance of fusion devices depends strongly on the chosen wall materials. Solid plasma-facing components (PFCs) are predominantly used in present devices, and are the most investigated candidates for fusion designs. High-Z materials such as tungsten (W) are the leading solid PFC material candidates. To date, a material choice that scales to steady-state reactor conditions has not been identified. Moreover, if plasma transient events such as edge-localized modes and disruptions cannot be altogether avoided or sufficiently mitigated, the projected peak heat and particle loads far exceed the power exhaust capabilities of solids. Liquid metal (LM) PFCs represent an intrinsic self-healing boundary that are both resilient to surface damage from transients, and that could handle high steady-state heat and particle fluxes. Flowing LM PFCs can be designed to remove “slag,” the buildup of material erosion due to plasma-material interactions, including charge exchange sputtering in the main chamber. Further, LM offer the prospect to manage hydrogenic species otherwise retained in the PFCs, which is important from a safety and inventory standpoint. The two most promising LMs are lithium (Li) and tin (Sn), although Sn–Li eutectics may be considered. While Sn offers a higher temperature window with low vapor pressure and low hydrogen retention, Li offers the prospect of enhanced energy confinement and higher acceptable core contamination limits, and this section focuses on Li PFCs. An LM PFC development research program developed LM PFC concepts for a nuclear fusion device via engineering design calculations, single-effect experiments, and staged prototypical experiments. A self-consistent design window was identified with liquid Li flow speeds ~5–10 m/s; plasma contamination was negligible for predicted Li evolution rates. While these preconceptual designs hold promise, there is substantial R&D needed to advance the technical readiness levels of LM PFCs for application to fusion power plants.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Connecting Femtosecond Transient Absorption Microscopy with Spatially Coregistered Time Averaged Optical Imaging Modalities

Multimodal all-optical imaging involving coregistered femtosecond transient absorption microscopy (TAM), time-integrated photoluminescence (PL), and steady-state modalities such as confocal reflectance and transmission offers an appealing approach to gain a comprehensive understanding of complex electronic excited-state phenomena in spatially heterogeneous systems. A unique combination of these modalities allows us to unravel not only the competing electronic excited-state dynamical processes but also the underlying morphological information with simultaneous high temporal and spatial resolution. However, correlating the various images obtained from time-resolved and time-independent modalities is generally nontrivial and particularly challenging when the electronic dynamics under study evolve in both time and space. Here, we demonstrate a new approach for rationally correlating time-resolved microscopy with coregistered time-integrated or steady-state modalities. Specifically, our approach involves an extended global lifetime analysis of the time-resolved microscopic data set to separate distinct dynamical processes taking place on commensurate time scales, and the resulting decay-associated amplitude maps (DAAMs) were applied to explore correlations with the images acquired using time-independent modalities. The feasibility of our approach was validated through analyzing a multimodal data set acquired from a thin film of chloride-containing mixed lead halide perovskites (CH 3 NH 3 PbI 3–x Cl x ) using femtosecond transient absorption, time-integrated PL, and confocal reflectance microscopies. Analysis of the results obtained enable us to gain new insight into the complex ultrafast relaxation dynamics in this highly heterogeneous system.

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

Polaron Delocalization in Donor–Acceptor Polymers and its Impact on Organic Electrochemical Transistor Performance

Abstract Donor–acceptor (D‐A) polymers are promising materials for organic electrochemical transistors (OECTs), as they minimize detrimental faradaic side‐reactions during OECT operation, yet their steady‐state OECT performance still lags far behind their all‐donor counterparts. We report three D‐A polymers based on the diketopyrrolopyrrole unit that afford OECT performances similar to those of all‐donor polymers, hence representing a significant improvement to the previously developed D‐A copolymers. In addition to improved OECT performance, DFT simulations of the polymers and their respective hole polarons also reveal a positive correlation between hole polaron delocalization and steady‐state OECT performance, providing new insights into the design of OECT materials. Importantly, we demonstrate how polaron delocalization can be tuned directly at the molecular level by selection of the building blocks comprising the polymers’ conjugated backbone, thus paving the way for the development of even higher performing OECT polymers.

Moser, Maximilian↗
DOE OSTI2021

Thermal loading analysis of the ring injection dump for the Spallation Neutron Source facility

The ring injection dump (RID) is the largest beam dump in the Spallation Neutron Source facility at Oak Ridge National Laboratory and accepts a fraction of the beam from the ring that is not captured in the ring during injection. Thermo-fluid modeling of the RID components was performed during the initial design by using the software ANSYS CFX to characterize the power rating for the RID. From the calculations, the power rating was lowered from 200 kW to 150 kW, at 1.3 GeV beam energy due to concerns regarding the heating of the concrete structure. The Proton Power Upgrade project scope included reevaluating the power limit to the RID in anticipation that increasing it would provide more operational flexibility. The focus was on the shielding because it was the limiting factor, and data collected from thermocouples installed on the structure were used to benchmark the analysis. A three-stage process was adopted in the latest study. First, the already existing steady-state calculations were validated and extended with the latest Monte Carlo N-Particle source term calculations. Second, transient calculations were conducted to capture the dynamic state of the system in response to the energy dumped to the RID during the following operational period of the beam from 2005–2019 (14 years), and sensitivity analyses of crucial parameters were performed to benchmark the model with reasonable accuracy. Finally, an idealized transient cycle analysis was conducted with realistic duty factors to predict the temperature distribution at higher beam powers. Overall, the results confirmed the accuracy of the original steady state model but allowed the development of a new validated transient model with higher accuracy for future analyses.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Comparison of excess free energy at an interface according to the applied interpolation scheme for elasticity: A phase-field method

Phase-field modeling is an effective simulation technique for modeling microstructure evolution of elastically anisotropic systems. To introduce the elastic energy contribution in a phase field model, an interpolation scheme is used to define the mechanical properties within the phases and across the continuous interface. Several existing interpolation schemes introduce a potential excess elastic energy at the interface, which undesirable effect on microstructure evolution needs to be evaluated. In this study, we focused on three interpolation schemes including Khachaturyan’ scheme (KHS), Voigt–Taylor’s scheme (VTS), and Steinbach–Apel’s scheme (SAS). Comparisons of these schemes’ performances were performed in three configuration types using the MOOSE (Multiphysics Object-Oriented Simulation Environment) framework: bi-crystal, isotropic particle-matrix and anisotropic particle-matrix. The contribution of excess elastic energy on the interface energy as a function of interface width and the computational time to steady-state were evaluated in these three configurations. SAS introduces the lowest excess elastic energy contribution and the VTS has the biggest contribution amongst the considered schemes. Moreover, when modeling precipitation in an anisotropic elastic material, the SAS approach seems to predict more physical convex shapes during growth, making it preferable to KHS and VTS. Finally, as currently implemented, SAS requires the largest computational time and KHS requires the smallest time to reach steady-state amongst the considered schemes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

$\mathrm{UPDATED}$ $\mathrm{U3SI2}$ thermal creep model and sensitivity analysis of the $\mathrm{U3SI2-SIC}$ accident tolerant $\mathrm{FUEL}$

U 3 Si 2 is a candidate accident tolerant fuel (ATF) replacement for UO 2 . U 3 Si 2 ’s high uranium density and high thermal conductivity are favorable properties in steady-state and accident conditions. Low power performance of this U3Si2-SiC concept fuel is compared to that of UO 2 -Zr4 fuels by implementing models that describe the properties of U 3 Si 2 and SiC-SiC into Idaho National Laboratory's (INL) fuel performance code, BISON. Included in these material models is a thermal creep model for U 3 Si 2 based on compressive creep data. The simulated results are in keeping with community knowledge that the U 3 Si 2 -SiC concept fuel may serve as a replacement for UO 2 -Zr4 fuels during steady-state operation, provided the mSiC layer remains under compression. Through a moderate power history and three 24-month fuel cycles, the mSiC layer remains under compressive stress through a burnup of 80 MWd/kgU. During low power operation, failure of the mSiC layer generally occurs prior to significant thermal creep in U 3 Si 2 . Generally, U 3 Si 2 creep is temperature sensitive and of little importance at the temperatures and stresses simulated during steady operation and during fuel-to-cladding contact. A parameter variation study including 11,520 individual simulations with variations in nominal fuel thermal creep rate, cladding thermal conductivity, cladding irradiation creep and swelling, cladding gap size, and cladding thickness demonstrated that research priorities for this ATF should revolve around reducing cladding thickness as a means to minimize cladding failure. Generally, despite advances in SiC-SiC compliance, the brittle nature of mSiC excludes U 3 Si 2 -SiC for use where fuel cladding contact may occur.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Transients following the loss of detonation confinement

We present a theory for the evolution of a one-dimensional, steady-state detonation reaction zone to a two-dimensional reaction zone, when the explosive experiences a sudden loss of side-on confinement as a boundary of the explosive is impulsively withdrawn. Our focus is on condensed-phase explosives, which we describe as having a constant adiabatic gamma equation of state and an irreversible, state-independent reaction rate. We consider two detonation models: (i) the instantaneous reaction heat release Chapman–Jouguet (CJ)-limit and (ii) the spatially resolved reaction heat-release Zel’dovich–von Neumann–Döring (ZND) model, in the limit where only a small fraction of the energy release is resolved (the SRHR-limit). Two competing rarefaction waves are generated by this loss of confinement: (i) a smooth wave coming off the full length of the withdrawn boundary and (ii) a singular fan spreading out from the point where the detonation shock and the withdrawn boundary meet. For the CJ-limit, in all cases the singular rarefaction fan eventually dominates the competition to control the steady-state behaviour. For the SRHR-limit, the spatially resolved heat release moderates this competition. When the withdrawal speed is fast, the rarefaction fan dominates; when the withdrawal speed is slower, the smooth rarefaction eventually dominates, although the flow features a fan at early times. By examining the mathematical properties of the steady two-dimensional fan-based solution, we set down a mechanism for this transition in behaviours.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Computationally inexpensive part-scale thermal history of additive friction-stir deposition

This study presents an analytical model for steady-state power generation and tool heat loss in additive friction-stir deposition (AFSD), developed to enable part-scale thermal simulation while remaining computationally inexpensive. The model predicts total generated power, yielding 3.7–4.7 kW across deposition temperature setpoints of 400–460 °C for the deposition of AA6061 with a Be-Cu tool. This corresponds to 90–95% of the reported spindle power. Tool heat loss is experimentally determined by calibrating a steady-state energy balance between the generated power, the substrate-deposition thermal gradient, and a temperature dependent tool heat loss term: q tool (T) = a + b (T - 400°C) with a = 2.7 x 10 6 Wm -2 and b = 9.5 x 10 3 Wm -2 K -1 . The calibration indicates that about 69% of the generated heat is conducted into the tool for this configuration, which is much higher than previously reported. The calibrated heat-source is implemented in finite element software (Adamantine) to simulate the transient thermal history of a 100 cm 3 representative build in 8 min on a standard desktop (at 0.635 mm build-height resolution). For the first three layers, the substrate temperatures between simulation and experiment are within 10% mean absolute percentage error. Sensitivity analysis indicates that uncertainties in average deposition temperature and deformation localization (stir-zone geometry, depth, and spatial dependance of strain-rate and flow stress) dominate model variance, motivating additional experimental verification.

Additive Friction-Stir Deposition↗
DOE OSTI2025

Reaction Pathways over ZnZrO 2 -Based Catalysts and Catalytic Sorbents

Reactive capture and conversion (RCC) is a process intensification approach that integrates CO 2 capture and hydrogenation within a single unit, removing the CO 2 purification and storage steps of traditional process flow schemes. This alters the catalytic step from a traditional steady-state (SS) flow process to a transient capture and conversion cycle, which could lead to product distributions distinct from those observed in conventional SS experiments. Such differences are investigated in the combined capture and hydrogenation of carbon dioxide to methanol over a ZnZrO 2 catalyst and a ZnZrO 2 + NaNO 3 /Mg 3 AlO x catalytic sorbent (CS) using fixed-bed kinetic measurements, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and steady-state isotopic transient kinetic analysis-DRIFTS (SSITKA-DRIFTS). Under SS conditions, ZnZrO 2 produced methanol through sequential hydrogenation of HCOO* and CH 3 O* intermediates. On the contrary, CO was attributed primarily to CO 2 dissociation at oxygen vacancies, as supported by isotopic shifts and measured reaction orders. For the CS, isotopic switching experiments suggested that monodentate carbonate species (CO 3 2− , abbreviated as m-CO 3 2− ) act as active intermediates that can be hydrogenated to HCOO* and subsequently to CH 3 O. Under RCC conditions, in situ DRIFTS and isotopic experiments reveal that m-CO 3 2− species formed during the CO 2 capture step follow two competing routes upon H 2 exposure: (i) direct hydrogenation to methane on the sorbent domain or (ii) migration of m-CO 3 2− to the ZnZrO 2 domain, where they are hydrogenated to methanol through the HCOO pathway. Overall, RCC enables carbonate hydrogenation routes not observed under SS cofeed conditions. Thus, the reaction pathways and rates during RCC can be different from operation under conventional SS conditions, and the product distribution is determined here by competition between carbonate hydrogenation on sorbent sites and migration to ZnZrO 2 for methanol synthesis.

CCUS↗