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At least 325 records · Page 18

High-resolution inelastic x-ray scattering at the high energy density scientific instrument at the European X-Ray Free-Electron Laser

We introduce a setup to measure high-resolution inelastic x-ray scattering at the High Energy Density scientific instrument at the European X-Ray Free-Electron Laser (XFEL). The setup uses the Si (533) reflection in a channel-cut monochromator and three spherical diced analyzer crystals in near-backscattering geometry to reach a high spectral resolution. An energy resolution of 44 meV is demonstrated for the experimental setup, close to the theoretically achievable minimum resolution. The analyzer crystals and detector are mounted on a curved-rail system, allowing quick and reliable changes in scattering angle without breaking vacuum. The entire setup is designed for operation at 10 Hz, the same repetition rate as the high-power lasers available at the instrument and the fundamental repetition rate of the European XFEL. Among other measurements, it is envisioned that this setup will allow studies of the dynamics of highly transient laser generated states of matter.

47 OTHER INSTRUMENTATION↗

Managing photoinduced electron transfer in AgInS2–CdS heterostructures

Ternary semiconductors such as AgInS2, with their interesting photocatalytic properties, can serve as building blocks to design light harvesting assemblies. The intraband transitions created by the metal ions extend the absorption well beyond the bandgap transition. The interfacial electron transfer of AgInS2 with surface bound ethyl viologen under bandgap and sub-bandgap irradiation as probed by steady state photolysis and transient absorption spectroscopy offers new insights into the participation of conduction band and trapped electrons. Capping AgInS2 with CdS shifts emission maximum to the blue and increases the emission yield as the surface defects are remediated. CdS capping also promotes charge separation as evident from the efficiency of electron transfer to ethyl viologen, which increased from 14% to 29%. The transient absorption measurements that elucidate the kinetic aspects of electron transfer processes in AgInS2 and CdS capped AgInS2 are presented. The improved performance of CdS capped AgInS2 offers new opportunities to employ them as photocatalysts.

Kipkorir, Anthony↗

Nucleotide- and metalloid-driven conformational changes in the arsenite efflux ATPase ArsA

Arsenite (As III ) is toxic to all organisms due to its ability to tightly bind exposed thiols within cells. An important As III resistance mechanism in prokaryotes involves proteins encoded by thearsoperon. A central component of thearsoperon in many bacteria is the cytoplasmic ATPase, ArsA, which orchestrates a series of nucleotide-dependent handoffs, starting with the capture of As III by the ArsD metallochaperone and culminating in its removal from the cell by the ArsB efflux pump. Although the mechanism of ArsA has been widely studied, the molecular details of how nucleotide hydrolysis modulates these events remain unclear. ArsA is an archetypal member of the intradimeric Walker A (IWA) family of ATPases, implicated in a diversity of complex biological functions. Conformational changes typical of IWA ATPases have been postulated to drive these molecular events but have not been demonstrated. We report cryogenic electron microscopy (cryo-EM) structures of ArsA in MgADP-bound and MgATP-boundopenstates, as well as a distinctclosedMgATP-bound state liganded to As III . X-ray absorption spectroscopy (XAS) confirmed three-coordinate binding of As III to the conserved cysteines at the metalloid-binding site of the closed state. Coupled with biochemical characterization, our cryo-EM structures reveal key conformational changes in the ArsA catalytic cycle consistent with other IWA ATPases and provide the structural basis for allosteric activation of nucleotide hydrolysis by As III . This work establishes how the nucleotide state of ArsA transiently creates a high-affinity binding site that can sequester metalloid within the cell, followed by a nucleotide-driven handoff to ArsB for efflux.

Science & Technology - Other Topics↗

Dynamic Model of Active Front-End Converters with 2DOF-PI Controllers for DC Bus Voltage Control

In most of the research, a conventional one degree-of-freedom type proportional-integral controller (1DOF-PI) is used for the regulation of the dc bus voltage in an Active Front-End Converter (AFEC). This paper proposes a two degree-of-freedom type proportional-integral controller (2DOF-PI) for the regulation of dc bus voltage in an AFEC. Such a controller eliminates the left-half plane (LHP) zero in the command-to-output transfer function for dc bus voltage regulation that is inherent to the conventional 1DOF-PI for this application. The dynamic model of an AFEC in the synchronous reference frame (SRF) is presented. An inner current control and outer dc voltage control loop is built for controlling the AFEC. Vector-control scheme is employed to achieve decoupled control of direct-axis and quadrature-axis currents. The outer dc voltage control loop is designed with a 2DOF-PI to complete the control system. Transfer function (TF) of the controller is derived based on the presented model and used to calculate the controller gains. Transient and steady state performance of the designed controllers are investigated in MATLAB/Simulink and results presented.

Thapa, Anup↗

A Hybrid Heavy Duty Diesel Power System for Off-Road Applications—Concept Validation

A multiyear power system R&D program was completed with the objective of developing an off-road hybrid heavy duty diesel engine with front end accessory drive-integrated energy storage. This system was validated to deliver 10.5–25.6% reduction in fuel consumption over current Tier 4 Final-based 18L diesel engines, over various off-road machine application cycles. The power system consisted of a downsized heavy-duty diesel 13L engine containing advanced combustion technologies, capable of elevated peak cylinder pressures and thermal efficiencies, thermal barrier coatings, exhaust waste heat recovery via SuperTurbo™ turbocompounding, and hybrid energy assisting and recovery through both mechanical and electrical systems. Following the concept definition, design, and analysis phases of the program, the final phase focused on building and validating the performance and efficiency in laboratory tests. While aspects of the system such as start/stop and reduced off-road cooling package energy losses were only analytically evaluated, the main 13L concept engine with full hybrid system was successfully built and tested in steady-state and in transient certification and real-world application cycles. Extensive simulations in Caterpillar's DYNASTY™ software environment utilized the validation test data to assess performance more fully and confidently over varied cycles and strategies. An average fuel consumption reduction of 17.9% was realized, and the majority (~13%) of the benefit stemmed from the core concept 13L engine. In conclusion, a total cost of ownership analysis provides context to commercial viability and where adoption focus should be placed.

33 ADVANCED PROPULSION SYSTEMS↗

Light-induced magnetization from magnonic rectification

Rectification describes the conversion of an oscillating field or current into a quasi-static one and the most basic example of a rectifier is an AC/DC converter in electronics. This principle can be translated to nonlinear light-matter interactions, where optical rectification converts the oscillating electric field component of light into a quasi-static polarization and phononic rectification converts a lattice vibration into a quasi-static structural distortion. Here, we present a rectification mechanism for magnetism that we call magnonic rectification, where a spin precession is converted into a quasi-static magnetization through the force exerted by a coupled chiral phonon mode. The transiently induced magnetic state resembles that of a canted antiferromagnet, opening an avenue toward creating dynamical spin configurations that are not accessible in equilibrium.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Universal phase dynamics in VO 2 switches revealed by ultrafast operando diffraction

Understanding the pathways and time scales underlying electrically driven insulator-metal transitions is crucial for uncovering the fundamental limits of device operation. Using stroboscopic electron diffraction, we perform synchronized time-resolved measurements of atomic motions and electronic transport in operating vanadium dioxide (VO 2 ) switches. We discover an electrically triggered, isostructural state that forms transiently on microsecond time scales, which is shown by phase-field simulations to be stabilized by local heterogeneities and interfacial interactions between the equilibrium phases. This metastable phase is similar to that formed under photoexcitation within picoseconds, suggesting a universal transformation pathway. Our results establish electrical excitation as a route for uncovering nonequilibrium and metastable phases in correlated materials, opening avenues for engineering dynamical behavior in nanoelectronics.

36 MATERIALS SCIENCE↗

Hyper-Differential Sensitivity Analysis of Uncertain Parameters in PDE-Constrained Optimization

Many problems in engineering and sciences require the solution of large scale optimization constrained by partial differential equations (PDEs). Though PDE-constrained optimization is itself challenging, most applications pose additional complexity, namely, uncertain parameters in the PDEs. Uncertainty quantification (UQ) is necessary to characterize, prioritize, and study the influence of these uncertain parameters. Sensitivity analysis, a classical tool in UQ, is frequently used to study the sensitivity of a model to uncertain parameters. In this article, we introduce "hyper-differential sensitivity analysis" which considers the sensitivity of the solution of a PDE-constrained optimization problem to uncertain parameters. Our approach is a goal-oriented analysis which may be viewed as a tool to complement other UQ methods in the service of decision making and robust design. We formally define hyper-differential sensitivity indices and highlight their relationship to the existing optimization and sensitivity analysis literatures. Assuming the presence of low rank structure in the parameter space, computational efficiency is achieved by leveraging a generalized singular value decomposition in conjunction with a randomized solver which converts the computational bottleneck of the algorithm into an embarrassingly parallel loop. Two multi-physics examples, consisting of nonlinear steady state control and transient linear inversion, demonstrate efficient identification of the uncertain parameters which have the greatest influence on the optimal solution.

97 MATHEMATICS AND COMPUTING↗

SAM Enhancements and Model Developments for Molten-Salt-Fueled Reactors

To support the development and utilization of the SAM code for molten-salt-fueled reactor (MSR) safety analysis and licensing, an effort was devoted to enhancing code capabilities and developing reference models for the MSR primary loop. A reference standard problem of a prototypical reactor design is foundational to NRC to verify the adequacy of computer codes and evaluation models for a specific reactor type. A thermo-fluid model of the Molten Salt Reactor Experiment (MSRE) has been developed. The MSRE primary loop model consists of a 2-D core region and external core components in 1-D or 0-D. Both the steady-state and a transient scenario are simulated. The porous medium model is utilized for both the molten salt fluid channels and the moderator matrix in the MSRE core. The use of the porous medium model for the MSRE core is verified with the higher-fidelity simulation results using 1-D representations of the fluid channels and 3-D modeling of core structures. To further enhance SAM multi-scale simulation capabilities for MSRs, a mass transport model is developed and implemented in SAM multi-dimension flow module for modeling of species transport such as delayed neutron precursors in MSRs.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Progress on Computational Modeling of Water-Based NSTF (FY2021)

This report documents the FY21 progress and achievements made in the computational analyses of the water-based NSTF. Both system-level and high-fidelity Computational Fluid Dynamics (CFD) analyses were performed to gain a complete understanding of the complex flow and heat transfer phenomena in natural convection systems. The progress on the waterbased NSTF experimental testing is summarized in a companion report (ANL-ART-230). As a continuation of progress from previous years, in FY21 the RELAP5 model of the NSTF was first updated to include a representative heated cavity that incorporated convection and conduction means of heat transfer. Two different cavity models were developed, one that models the radiation heat exchange among all surfaces in one enclosure (Cavity Model 1), and another that employs multiple radiation enclosures with each considering the surfaces at one axial level (Cavity Model 2). This updated RELAP5 deck was benchmarked with single-phase test data to tune form loss coefficients of the elbows and tees, along with heat transfer coefficients within the cavity and off the external insulation panels. This tuned model was then found to accurately predict fluid temperatures within 2.5% and both system and riser flow rates within 6% during single-phase, steady-state simulations. For transient simulations, there is a slight over prediction of the flow rate, fluid temperatures, and heater temperatures during the heat-up period, which indicate that the transient heat loss may be underestimated. Following, the capabilities of RELAP5-3D were examined, which feature a conduction enclosure model that is not present in the current version of RELAP5-MOD3.3 used for all previous NSTF simulations. As an initial comparison of the two codes, single-phase simulations were run that used similar input decks. The results indicate that the single-phase flow predicted by the two codes was very similar, however RELAP5-3D appears to predict a higher system flow during the two-phase transient when compared to the flow rates predicted by RELAP5-MOD3.3. Furthermore, RELAP5-3D run did not capture the density wave oscillations or geysering phenomena, which are large oscillation flow instabilities observed in the experimental facility. To further the prediction capabilities for capturing two-phase instabilities, Options 55, 57, 58, 61, which are implemented by default in RELAP5-MOD3.3 but not in RELAP5-3D, were investigated. When enabling Option 61, RELAP5-3D agrees well with MOD3.3 in predicting the total system flow, while other options have negligible effect on the predicted total system flow by RELAP5-3D. However, none of these options enables RELAP5-3D to produce the same flow instabilities. For future steps, efforts are currently underway to investigate RELAP5-3D’s different behavior in predicting low-pressure two-phase instabilities. STAR-CCM+ was used to perform CFD analysis of the water-based test facility and provide simulation results for comparisons to experimental data. Efforts first focused on describing the characteristics of flow within the heated cavity. A study was performed on whether possible leakage flow between the two sides of the cavity could substantially impact and explain the results. An additional second assumption was examined which defined adiabatic side walls, so physical insulation structures were added to the models to allow conduction across this outer insulation. The results suggest that potential porosity of the insulation could be a major factor in the temperature distribution within the cavity and should be considered in any studies where it is desirable to know the cavity wall temperatures to higher accuracy.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Design and Testing of a Water-Cooled Rotating Detonation Combustor at Elevated Operating Pressures - Abstract

This is an extended abstract being submitted for consideration that briefly describes the material that will be included in the final paper. This study will detail the design and testing of a water-cooled Rotating Detonation Combustor (RDC) that permits operation for extended periods of time ensuring that the device has reach a stable operating temperature. Extended run times also provides an opportunity to consider transient behaviors that occur as a result of altering the operating conditions such as equivalence ratio. The experimental setup is also unique in that it consists of a ducted exhaust with a downstream high-temperature valve that can control the pre-combustion pressure in the RDC independent of the combustor annulus and exit geometry. This paper will examine the results from the extended operation of the water-cooled RDC over a range of both transient and steady state equivalence ratios (0.5 - 1.0), pre-combustion operating pressures (0 - 207 kPa), mass flow rates (0.42 – 0.5 kg/sec) and air inlet throat area to combustor channel area ratios (0.09 – 0.32). All tests were performed while operating on hydrogen in air at a nominal air inlet temperature of 340 – 350 K. Limited data obtained at an elevated inlet air temperature of 480 K will also be discussed. Results suggest that under certain conditions the operating mode of the detonation wave can vary as it approaches a stable operating temperature. For the RDC tested, a stable operating temperature is not achieved until approximately 8-10 seconds of run time.

Ferguson, Donald↗

Multiphysics analysis of fuel fragmentation, relocation, and dispersal susceptibility–Part 1: Overview and code coupling strategies

The US nuclear energy industry is investigating strategies to increase the reactor operating cycle to 24 months, resulting in peak rod average burnups exceeding the current limit of 62 GWd/tU. This increase will in turn increase the probability of fuel fragmentation, relocation, and dispersal (FFRD) in the event of a loss-of-coolant accident (LOCA). This effort couples multiple codes to (1) evaluate full-core power histories for high-burnup fuel operated in a Westinghouse 4-loop pressurized water reactor, (2) model a postulated large-break LOCA, and (3) calculate the mass of fuel susceptible to FFRD. This paper, the first of three describing the work, focuses on code coupling strategies and FFRD susceptibility calculations. The other two companion papers focus on code-specific designs and analyses. Three codes were used in this work. VERA was used to calculate steady-state power histories, TRACE was used to model the transient thermal hydraulics, and BISON was used to model steady-state and transient fuel performance and cladding failure. Herein, several fuel pulverization models were used to calculate FFRD susceptibility in failed rods. Depending on the cladding failure/fuel pulverization model combination, the core-wide FFRD susceptibility during the postulated LOCA range from 0 to over 5,000 kg.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The Radiation-Induced Fate of Fission Product Iodine in Molten Salts

Understand and Predict Radiation-Induced Iodine Speciation, Chemistry, and Transport in High-Temperature Molten Salts Award Number: DE-AC07-05ID1451 Gregory P. Holmbeck (Gregory.Holmbeck@inl.gov), Center for Radiation Chemistry Research, Idaho National Laboratory, 1955 N. Fremont Avenue Idaho Falls, ID, 83415, USA. Project Scope The goal of this Chemical and Materials Sciences to Advance Clean Energy Technologies and Low-Carbon Manufacturing project is to understand and predict the radiation-induced speciation, chemistry, and transport of fission product iodine in the triumvirate extremes of high-temperature, ionizing radiation, and corrosive molten salts. This missing fundamental information is critical for the accelerated development and deployment of safe, clean nuclear energy based on molten salt reactor (MSR) and pyrochemical reprocessing technologies. The central hypothesis driving this research is, the radiation-induced conversion of iodide will yield an extensive suite of transient and steady-state iodine radiolysis products that will alter the bulk chemical and physical properties of the irradiated molten salt system—the speciation, distribution, and chemical transport of which will be dictated by the composition and the availability of multivalent metal cations and metal alloy interfaces. To test this hypothesis, this project initiated three synergistic Research Objectives: (1) determine how the inclusion of iodine/iodide influences the chemical and physical properties of complex molten salt mixtures; (2) elucidate the speciation and fundamental chemical behavior of transient and steady-state iodine/iodide species formed by the irradiation of molten and solid salt mixtures; and (3) understand the influence of interfacial processes on determining the final disposition of iodine in high temperature molten salts, notably the structure and chemical speciation of iodine at metal-salt interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ligand-Structure-Dependent Coherent Vibrational Wavepacket Dynamics in Pyrazolate-Bridged Pt(II) Dimers

Bimetallic transition metal complexes have gained increasing attention because of their versatile functions in solar energy conversion and photonics applications arising from inter-metal electronic coupling. In bimetallic platinum (Pt) complexes, electronic communication between the Pt-centered and ligand-centered moieties have been shown to be critical for defining their excited-state dynamic trajectories undergoing either localized ligand centered (LC)/metal-to-ligand-charge-transfer (MLCT) transitions or delocalized metal-metal-to-ligand-charge-transfer (MMLCT) transitions. The branching of the excited-state intersystem crossing (ISC) trajectories are modulated through structural factors that alter the relative energies of the different states. In this study, we investigated the correlation of the structural factors influencing the excited state trajectories. Using femtosecond broadband transient absorption (fs-BBTA) spectroscopy, ultrafast dynamics in the excited state of two select Pt(II) dimers have been mapped out using their coherent vibrational wavepacket signatures in corresponding transient absorption spectra. To examine how the ligand moieties of the Pt(II) dimers influence excited-state dynamics and the coherent vibrational wavepacket behavior, here we carried out comparative studies on two pyrazolate-bridged Pt(II) dimers of the general formula [Pt( t Bu 2 Pz)(N^C)] 2 ( t Bu 2 Pz = 3,5-di-tert-butylpyrazole); N^C = 7,8-benzoquinoline (bzq, 1) or 1-phenylisoquinoline (piq, 2)). We found that photoexcitation into the low energy absorption bands of 1 and 2 respectively induce the formation of 1 MMLCT states from which ultrafast ISC proceeds, resulting in stimulated emission quenching and decoherence of the vibrational wavepacket motions. The results obtained in this study suggest that both energetics and the structural rigidity of the aromatic cyclometalating ligands in 1 and 2 can significantly influence dynamics along the excited state trajectory characterized by dephasing of the coherent oscillations. The collective results provide direct evidence of how ligand structure alters electronic dynamics along excited state trajectories associated with ISC processes, providing insight into using ligand design to steer photochemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Compatibility of divertor detachment and ELM suppression in DIII-D high- β p plasmas with ITER-similar shape

Abstract Integration of transient and steady-state divertor heat fluxes control with a high-performance core is necessary for future fusion reactors. In recent DIII-D high- β p experiments, divertor detachment and simultaneous edge localized mode (ELM) suppression are demonstrated while the plasma confinement quality is maintained high in ITER-similar shape. By optimizing the neon injection in high- β p scenario with ITER-similar shape, deep detachment and ELM suppression are achieved with a high-performance core ( β N ∼ 2.8, β p ∼ 2.3) at q 95 ∼ 7.5. Partial divertor detachment and suppression of large ELMs are achieved at q 95 ∼ 6. The stability analyses suggest that with low neon injection, the density pedestal becomes higher and steeper and the T i profile also increases, therefore the increased edge pressure and higher current density destabilize the Peeling-Ballooning mode (PBM), which would lead to a large ELM collapse. With strong neon gas puffing, the significantly reduced pedestal pressure and current density, due to the degraded T e pedestal, lead to the stabilization of PBM and ELMs are suppressed. For both cases, the coupling between the large radius internal transport barrier (ITB) and edge pedestal is the key reason for maintaining high global performance. The formation of large radius ITB compensates for pedestal degradation. Such results could provide an attractive scenario to well control the transient and steady-state heat flux onto the divertor plates while maintaining good plasma performance, which is an important step toward the steady-state operation of future fusion reactors.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Structure and Dynamics of Domains in Ferroelectric Nanostructures – Phase-Field Modeling (Final Technical Report)

Domain pattern formation is one of the most common phenomena in nature and is a topic of immense interest in many fields ranging from materials science and physics to chemistry and biology. This DOE sponsored research project explored the basic science concerning the thermodynamic stability of mesoscale polarization domain patterns and their temporal evolution mechanisms during formation and subsequent switching in ferroelectric nanostructures and heterostructures. The project employed the computational phase-field method in combination of microelasticity and electrostatic theories. The research was carried out in close collaboration with a number of experimental groups who used High Resolution Transmission Electron Microscopy (HRTEM), in situ TEM with Scanning Probe Microscopy (SPM), or Piezoresponse Force Microscopy (PFM) to characterize the domain structures and dynamics of ferroelectric thin films and heterostructures and who grow high-quality ferroelectric and multiferroic thin films using advanced growth techniques such as Molecular Beam Epitaxy (MBE), Pulsed Laser Deposition (PLLD), and sputtering. The research efforts of the project help establish the phase-field method as the most powerful method for understanding and predicting domain structures in ferroelectric thin films and nanostructures. The findings of the project led to the basic understanding of stability and switching mechanisms of ferroelectric domains under different mechanical boundary conditions and under either homogeneous capacitor configurations or local fields using metallic probes as electrodes and the emergence of charged domain walls during domain switching. The project predicted the spatial length scales, temperature ranges, and electromechanical conditions for different polar states in heterostructures and guided the discovery of both transient and stable novel polarization states containing vortex lattices in oxide superlattices. The project resulted in 134 journal publications and 6 PhD theses with all the PhD graduates currently working in either academia or industry within the United States. The basic understanding on the stability of mesoscale polar states and pattern evolution achieved by the project improved our ability to control and engineer properties of ferroelectric thin films and heterostructures for potential applications in nanoscale electronic devices.

36 MATERIALS SCIENCE↗

Synchrotron based transient x-ray absorption spectroscopy for emerging solid-state energy materials

The rational design of cutting-edge materials for an efficient solar energy conversion process is a challenging task, which demands a fundamental understanding of the mechanisms operative during the photoinduced physical and chemical reactions. In response to these issues, progress in the field has steered attention toward the use of time-resolved spectroscopic techniques to resolve the multiple intermediate species involved in these photoinduced reactions. Thanks to the advent of pump–probe technique, which leads to the development of various time-resolved spectroscopic methods, significant progress has been made in understanding the photophysical and photochemical properties (e.g., excited state dynamics, charge transfer mechanism, charge separation dynamics, etc.) of energy materials. Synchrotron-based x-ray transient absorption (XTA) spectroscopy is one of the most important time-resolved techniques to unravel the direct correlation of the material structure with their photophysical properties owing to its unique capability in directly observing electronic and structural evolution simultaneously. As a result, the aim of this work is to provide a systematic overview of the recent progress in using XTA for capturing the structural dynamics associated with excited state and charge separation dynamics in emerging solid-state energy materials.

14 SOLAR ENERGY↗

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↗