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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 811 records · Page 45
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Development of a high-fidelity multi-physics coupling between MCNP6.2 and CTF4.0 for VVER applications

Ensuring system safety in the design, licensing, and operation phases is a priority in the nuclear industry. Performing extensive, full-scale reactor safety experiments is often prohibitive due to the large associated costs. Computational simulations offer an alternative safety analysis method, typically with significant cost reductions. Recent high-level developments in technology and increased availability of computational resources have allowed the development of high-fidelity, high-resolution multi-physics coupled codes. Such developments may be used to generate reference models for deterministic core calculations. Under this framework, the high-fidelity continuous energy Monte Carlo-based neutron transport code MCNP6.2 was coupled externally with the state-of-the-art thermal-hydraulics subchannel code, CTF4.0 for VVER (Water-Water Energetic Reactor) applications. A VVER-1000 fuel assembly model was used to demonstrate the capability of the coupled code. The converged coupled solution is compared to initial results, consisting of the first MCNP evaluation and first CTF evaluation after initialization. The VVER-1000 type assembly results are compared to other evaluations of the same assembly model. The findings indicate good agreement with expectations and reference cases, where available. The initial results of the coupled MCNP6.2/CTF4.0 calculations at the assembly level for steady-state calculations are presented in this study, which may support future work toward high-fidelity coupled full-core modeling capabilities. The multi-physics model may be further improved, enhanced, and expanded for both cycle depletion and transient applications. Such a multi-physics system will also be applicable to the VVER-1200 and other triangular lattice designs and support their deployment and operation safely and economically. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2025

Multifunctional Catalysts for the Tandem Reactions of Oxygenates

Industrially-relevant catalytic reactions rarely consist of a simple sequence of elementary steps. Moreover, kinetic coupling of multiple reactions on a catalyst surface is highly desired for process intensification and improved energy efficiency for large scale chemical transformations. The shifting landscape of hydrocarbon chemical feedstocks in the US also motivates research on the selective conversion of more complex molecules. One desirable type of catalytic reaction is the reduction of carboxylic acids that are produced from biomass feedstocks to their corresponding alcohols. The proposed research explores the fundamental importance of hydrogen spillover on a multifunctional catalyst for carboxylic acid reduction with H 2 composed of metal particles coupled to metal oxide particles. Recent work has demonstrated the excellent performance of supported tungsten oxide clusters for carboxylic acid reduction, but only after they are promoted with a late transition metal such as palladium. Elucidating the active state of the catalyst and the associated reaction mechanism for acid reduction on that active state are the overall goals of the proposed project and successful completion will enable future design of efficient multifunctional catalysts. The critically important role of the metal promoter is hypothesized to be its ability to dissociate H2 and spillover atomic H to the support. Although hydrogen spillover is a well-recognized phenomenon in catalysis, its role in both catalyst activation and catalytic turnover are still unresolved. The study combined materials synthesis, characterization, reactivity testing, and molecular simulations, to explore the effect of hydrogen chemical potential on the formation of the active catalytic sites and on the steady state catalytic reduction of carboxylic acid. Varying the hydrogen chemical potential through modification of the gas conditions, support composition, and metal loading to modulated the structure and catalytic performance of the reducible metal oxide. Dual function catalysts containing supported Pd and WO x species co-located on a non-reducible carrier (silica) and a reducible carrier (titania) were synthesized and characterized by electron microscopy, temperature-programmed reduction, and chemisorption. Spectroscopic methods such as X-ray absorption and UV-vis were also used to evaluate the catalysts, which were used in the reduction of propionic acid to aldehyde and alcohol. Quantum chemical calculations, including ab initio phase diagrams provided molecular insights into the H spillover phenomenon.

09 BIOMASS FUELS↗
DOE OSTI2023

Rapid Electron Transfer Self-Exchange in Conformationally Dynamic Copper Coordination Complexes

Here we report the electron transfer (ET) self-exchange rate constants (k 11 ) for a pair of Cu II/I complexes utilizing dpa R (dpa = dipicolylaniline, R = OMe, SMe) ligands assessed by NMR line-broadening experiments. These ligands afford copper complexes that are conformationally dynamic in one oxidation state. With R = OMe, the Cu I complex is dynamic, while with R= SMe, the Cu II complex is dynamic. Both complexes exhibit unexpectedly large k 11 of 2.48(6) x 10 5 and 2.21(9) × 10 6 M –1 s –1 for [CuCl(dpa OMe )] +/0 and [CuCl(dpa SMe )] +/0 , respectively. Among the fastest reported for molecular copper coordination complexes to date, that of [CuCl(dpa SMe )] +/0 exceeds all others by an order of magnitude and compares only to those observed in type 1 blue copper proteins. The dynamicity of these complexes establish pre-steady-state con-formational equilibria that minimize the inner sphere reorganization energies to 0.71 and 0.62 eV for R = OMe and SMe, respectively. In contrast to the emphasis on rigidity in the formulation of entatic states applied to blue copper proteins, the success of these two systems highlight the relevance of conformational dynamicity in mediating rapid ET.

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

Local models of two-temperature accretion disc coronae – II. Ion thermal conduction and the absence of disc evaporation

We use local stratified shearing-box simulations with magnetic field-aligned thermal conduction to study an idealized model of the coupling between a cold, radiatively efficient accretion disc, and an overlying, hot, two-temperature corona. Evaporation of a cold disc by conduction from the hot corona has been proposed as a means of mediating the soft-to-hard state transitions observed in X-ray binary systems. We model the coronal plasma in our local disc patch as an MHD fluid subject to both free-streaming ion conduction and a parametrized cooling function that captures the collisional transfer of energy from hot ions to colder, rapidly cooling leptons. In all of our models, independent of the initial net vertical magnetic flux (NF) threading the disc, we find no evidence of disc evaporation. The ion heat flux into the disc is radiated away before conduction can heat the disc’s surface layers. When an initial NF is present, steady-state temperature, density, and outflow velocities in our model coronae are unaffected by conduction. Instead of facilitating disc evaporation, thermal conduction is more likely to feed the disc with plasma condensing out of the corona, particularly in flows without NF. Our work indicates that uncertainties in the amount of NF threading the disc hold far greater influence over whether or not the disc will evaporate into a radiatively inefficient accretion flow compared to thermal conduction. We speculate that a change in net flux mediates disc truncation/evaporation.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Demonstrating Computational Equivalence Between Continuous and Discrete Adjoint Methods by Calculating Time-Dependent Adjoint Solutions with Neutron Diffusion Models

The continuous adjoint method and the discrete adjoint method are two alternative approaches used to calculate adjoint solutions for adjoint systems. The continuous adjoint method derives adjoint equations analytically from continuous forward equations and then solves the adjoint equations either analytically or numerically in a discretized form whereas the discrete adjoint method calculates the adjoint solutions directly from the discretized forward equations. With regard to the methodology development and calculation procedure, distinct differences are well recognized between the two methods. For certain reasons, both methods are exclusively preferred and commonly used by different computational communities, but limited studies clarify the connections between the two adjoint methods from either of the communities. Herein, this paper demonstrates the computational equivalence between the continuous and discrete adjoint methods by investigating time-dependent adjoint solutions to the two-group neutron diffusion model in nuclear reactor analysis problems using both methods. Adjoint solutions can be used to estimate system parameters for reactor safety analysis. Appropriate final state conditions for the adjoint systems are specified in both of the methods, and the conditions are clarified with proper physical explanations. With the help of an event-based case study on neutron diffusion models, the accuracy of the time-dependent adjoint fluxes obtained from both methods is verified, and the pros and cons of both adjoint methods are examined. More importantly, the computational equivalence of both methods is demonstrated when they are applied to multigroup neutron diffusion systems. The advantage of calculating time-dependent adjoint fluxes by directly solving time-dependent adjoint systems rather than taking steady-state approximations as in common practice is also demonstrated.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Cyclic superconducting refrigerators using guided fluxon propagation

We propose cyclic refrigeration in solid state, employing a gas of magnetic field vortices in a type-II superconductor—also known as fluxons—as the cooling agent. Refrigeration cycles are realized by envisioning a racetrack geometry consisting of both adiabatic and isothermal arms, etched into a type-II superconductor. The guided propagation of fluxons in the racetrack is achieved by applying an external electrical current, in a Corbino geometry, through the sample. A gradient of magnetic field is set across the racetrack allowing one to adiabatically cool down and heat up the fluxons, which subsequently exchange heat with the cold and hot reservoirs, respectively. We characterize the steady state of refrigeration cycles thermodynamically for both s -wave and d -wave pairing symmetries, and present their figures of merit such as the cooling power delivered, and the coefficient of performance. Our cooling principle can offer significant cooling for on-chip microrefrigeration purposes, by locally cooling below the base temperatures achievable in a conventional dilution refrigerator. We estimate n W / m m 2 of cooling power per unit area assuming a tunnel coupling with ∼ M Ω µ m 2 specific resistance. Integrating the fluxon fridge to quantum circuits can enhance their coherence time by locally suppressing thermal fluctuations, and improve the efficiency of single photon detectors and charge sensors. Published by the American Physical Society 2024

Karmakar, Tathagata (ORCID:0000000187812017)↗
DOE OSTI2024

Predicting Radiation-Induced Plutonium Redox Chemistry using Multi-scale Modeling Methods

Over the the last 70 years plutonium (Pu) has been integral in the development of several technologies that have changed the world, yet our fundamental understanding of its chemistry is still far from complete. This is a testament to this element’s unique and complex properties, such as its ability to coexist as multiple oxidation states in aqueous solution. Careful manipulation of plutonium oxidation states is essential in the study and utilization of its rich chemistry. To achieve this level of control, a comprehensive mechanistic understanding of radiation-induced plutonium redox chemistry is critical due to the unavoidable exposure of plutonium to ionizing radiation fields, both inherent and from in-process applications. For this reason, we have developed an experimentally evaluated multi-scale computer model for the prediction of gamma radiation-induced Pu(IV) redox chemistry in concentrated nitric acid solutions (1.0, 3.0, and 6.0 M). Under these acidic, aqueous solution conditions, cobalt-60 gamma irradiation afforded negligible net change in the steady-state oxidation state distribution of Pu(IV). Multi-scale calculations, which are in excellent agreement with experimental data, indicate that this observation is due to radiation-induced redox cycling between Pu(IV) and Pu(III), as achieved by the reduction of Pu(IV) by radiolytic nitrous acid and hydrogen peroxide, and the oxidation of Pu(III) by nitrate and hydroxyl radicals. These radiation-induced redox processes are augmented by plutonium’s inherent disproportionation reactions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Triple Emission of 5'-( para -R-Phenylene)vinylene-2-(2'-hydroxyphenyl)benzoxazole (PVHBO). Part II: Emission from Anions

This paper is the second part of a study on the effects of a substituted 5'-phenylenevinylene (PV) functionality on the emission properties of 2-(2'-hydroxyphenyl)benzoxazole (HBO)-a dye that is known for excited-state intramolecular proton transfer. The topical compounds are referred to as PVHBOs, each of which is a structural fusion of HBO and a 4-hydroxy-4'-R-stilbene fluorophore that occurs at the hydroxyphenyl moiety. Therefore, the resulting fusion fluorophore manifests the properties of one component or the other, as governed by its interactions with the environment. In part I (the preceding paper), PVHBOs are divided into two groups depending on whether the R substituent is electron-donating/neutral (group I) or electron-withdrawing (group II). The difference in absorption and emission properties between groups I and II is explained based on observations from spectroscopic experiments (both steady-state and time-resolved) and quantum chemical calculations. In the current paper, the same set of tools is applied to characterize the photophysical properties of the conjugate bases-that is, the anions-of PVHBOs. The emission energy of the anion of any group I compound, where the R substituent is either electron-donating or neutral, is situated between those of the neutral enol and keto forms. The emission of the anion of any given group II compound, on the other hand, has a lower energy than both the enol and keto emissions. In this work, the frontier molecular orbitals (i.e., HOMO, LUMO, and LUMO + 1) of a PVHBO localized on either HBO or stilbenoid are impacted by the substituent R and the solvent/additive differently, which leads to the differences in the optical properties of group I and II PVHBOs in both neutral and anion forms.

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

Preliminary Implementation of Two-Dimensional Cartesian Solver in CTF-R

Sub-channel codes are one of the the modeling and simulation tools used for thermal-hydraulic analysis of nuclear reactors. A few examples of such sub-channel codes are the COolant Boiling in Rod Arrays (COBRA) family of codes. The approximations that are used to simplify the fluid conservation equations into sub-channel form, mainly that of axially-dominated flow, lead to noticeable limitations on sub-channels solvers for problems with significant flow in lateral directions. In this report, a two-dimensional Cartesian solver is developed and implemented within CTF-R, which is the residual solver in the North Carolina State University version of COBRA-TF (CTF). The new solver will enable CTF to simulate flow that is not axially-dominated. The appropriate Cartesian forms of the conservation equations are derived and implemented in the solver. Once the conservation equations are established, the process of constructing the matrix system was altered to solve a two-dimensional staggered grid system. A simple case was used to test that the two-dimensional Cartesian solver is accurate. The test problem does not include any source terms or flow in the lateral direction. The results show that the solver was able to run the simple case and converge to a steady-state solution. Future work will focus on testing existing capabilities by using test cases that include transients and equation cross-terms. Future work will also include adding additional capabilities such as enabling the solver to include cases with source terms and three dimensional cases.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2026

Temporal entanglement transitions in the periodically driven Ising chain

Periodically driven quantum systems can host non-equilibrium phenomena without static analogs, including in their entanglement dynamics. Here, we discover (TET) in a Floquet spin chain, which correspond to a quantum phase transition in the spectrum of the entanglement Hamiltonian and are signaled by dynamical spontaneous symmetry breaking. We identify the symmetry principles underlying these transitions: they appear when the driven Hamiltonian preserves global symmetry (here, ℤ2), the initial state respects this symmetry, and the reduced density matrix carries weight in both subsystem-parity sectors, with TET occurring precisely when the sector weights become equal (given the previous two conditions are also satisfied). Intriguingly, we find these transitions across a broad range of driving frequencies (from adiabatic to high-frequency regime) and independently of drive details, where they manifest as periodic, sharp entanglement spectrum reorganizations marked by the Schmidt-gap closure, a vanishing entanglement echo, and symmetry-quantum-number flips, while remaining invisible to conventional local observables. At high frequencies, the entanglement Hamiltonian acquires an intrinsic timescale decoupled from the drive period, rendering the transitions genuine steady-state features. Finite-size scaling reveals universal critical behavior with correlation-length exponent 𝜈 = 1, matching equilibrium Ising universality despite its emergence from purely dynamical mechanisms decoupled from static criticality. Furthermore, our work establishes TET as novel features in Floquet quantum matter.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Degradation Mechanisms in Advanced MEAs for PEM Water Electrolyzers Fabricated by Reactive Spray Deposition Technology

Proton exchange membrane water electrolyzers (PEMWEs) have demonstrated enormous potential as the next generation hydrogen production technology. The main challenges that the state-of-the-art PEMWEs are currently facing are excessive cost and poor durability. Understanding the failure modes in PEMWEs is a key factor for improving their durability, lowering the precious metal loading, and hence cost reduction. Here, reactive spray deposition technology (RSDT) has been used to fabricate a membrane electrode assembly (MEA) with one order of magnitude lower Pt and Ir catalyst loadings (0.2–0.3 mg PGM cm –2 ) in comparison to the precious metal loadings in the stat-of-the-art commercial MEAs (2–3 mg PGM cm –2 ). As fabricated MEA with an active area of 86 cm 2 , has been tested for over 5000 h at steady-state conditions that are typical for an industrial hydrogen production system. Herein, we present and discuss the results from a comprehensive post-test analysis of the MEA of interest. The main degradation mechanisms, governing the performance loss in the RSDT fabricated MEA with ultra-low precious metal loadings, have been identified and discussed in detail. All failure modes are critically compared and the main degradation mechanism with the highest impact on the MEA performance loss among the others is identified.

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

The saturation mechanism of thermal instability

The literature on thermal instability (TI) reveals that even for a simple homogeneous plasma, the nonlinear outcome ranges from a gentle reconfiguration of the initial state to an explosive one, depending on whether the condensations that form evolve in an isobaric or nonisobaric manner. After summarizing the recent developments on the linear and nonlinear theory of TI, here we derive several general identities from the evolution equation for entropy that reveal the mechanism by which TI saturates; whenever the boundary of the instability region (the Balbus contour) is crossed, a dynamical change is triggered that causes the comoving time derivative of the pressure to change the sign. This event implies that the gas pressure force reverses direction, slowing the continued growth of condensation. For isobaric evolution, this “pressure reversal” occurs nearly simultaneously for every fluid element in condensation and a steady state is quickly reached. For nonisobaric evolution, the condensation is no longer in mechanical equilibrium and the contracting gas rebounds with greater force during the expansion phase that accompanies the gas reaching the equilibrium curve. The cloud then pulsates because the return to mechanical equilibrium becomes wave mediated. We show that both the contraction rebound event and subsequent pulsation behavior follow analytically from an analysis of the new identities. Our analysis also leads to the identification of an isochoric TI zone and makes it clear that unless this zone intersects the equilibrium curve, isochoric modes can only become unstable if the plasma is in a state of thermal non-equilibrium.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

First feedback-controlled divertor detachment in W7-X: Experience from TDU operation and prospects for operation with actively cooled divertor

In the last experimental campaign (OP1.2b) of the stellarator Wendelstein 7-X (W7-X), boronisation as a mean for first wall conditioning was applied for the first time which led to strongly reduced impurity fluxes from plasma-facing components. Thermal detachment at the uncooled target plates of the test divertor unit (TDU) was reached at higher plasma densities and was accompanied by high recycling of neutrals at the target plate. A feedback control system was established in W7-X to actively control the gas injection (actuator) for plasma fuelling and impurity seeding [3] through the divertors. It allowed very successful stabilisation of the detached plasma condition state as well as mitigation of thermal overloads to some baffle tiles. Different routinely available diagnostic signals were used as input parameters (sensors). We describe the setup of the feedback control system, its performance and provide some example results with the main focus on the development of the control scheme which led to the detachment stabilisation over the entire longest (30 s) high-power discharge at W7-X so far. In view of the achieved very successful detachment stabilisation and the necessity to include simultaneous optimisation of the core performance in the future, the feedback control system is being upgraded for the upcoming campaign (OP2.1) in which the water cooled and hereby inherently steady-state capable divertor has been currently installed. The prospects and some experiment ideas for active detachment control are discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Evaluating Hydropower Plants for Wildfire Resilient Microgrids

The increasing occurrence and severity of wildfires in recent years is severely impacting critical infrastructures, including the power grid, compromising the quality of life and provision of essential services, including electricity. The western parts of the United States, more specifically Washington, Oregon, and California, which are prone to large wildfires, are also rich in hydropower resources. Hydropower resources located close to communities vulnerable to wildfire can be utilized to develop wildfire-resilient microgrids to support critical needs of those communities. Therefore, this paper develops a framework to characterize hydropower plants and evaluate their feasibility to operate in microgrids during wildfire-related outages. In the proposed framework, hydropower plants are characterized using various plant and site attributes and evaluated in terms of capability and performance indicative metrics. A case study is carried out evaluating the Hills Creek hydropower plant located in a wildfire-prone region of Oregon for wildfire-resilient microgrid. The results of steady-state and dynamic simulations show that the hydropower plant is capable of providing the essential microgrid services and powering nearby communities during extended wildfire-related outages.

29 - ENERGY PLANNING, POLICY AND ECONOMY↗
DOE OSTI2021

Microstructural Evolution During a Solid State Tube Pinch Weld of Type 304l Stainless Steel

Microstructure development is examined for a specialized spot weld that is used as a solid-state closure process for austenitic stainless steel tubing, referred to as pinch welding. In order to elucidate the microstructural evolution of the weld, a series of test welds were made at nominal conditions using tubing and production like components. These pinch welds normally terminate after twelve cycles of a 60 Hz AC weld process. In this study, production tubes were welded from one to twelve cycles and the microstructure and weld variables after each individual weld cycle number were characterized using radiography and optical metallography. Two electrochemical etchants were used to highlight different microstructural features. The study revealed that: (1) this type pinch weld is largely complete after about six cycles of 60 Hz AC current, half the weld time utilized; (2) the resistance, deformation, and closure length approach “steady-state” conditions after six cycles; and (3) both oxalic and nitric acid electrolytic etchants are useful for highlighting specific microstructural attributes of type 304 L stainless steel. Finally, two distinct microstructural regions can be identified for these welds: the edge of the weld, which is driven by concentrated deformation, recrystallization, and grain growth, and the center region, which is more typical of forge welding and micro-asperity breakdown followed by diffusion and grain-growth.

36 MATERIALS SCIENCE↗
DOE OSTI2023

FEOTS v0.0.0: a new offline code for the fast equilibration of tracers in the ocean

Abstract. In this paper we introduce a new software framework for the offline calculation of tracer transport in the ocean. The Fast Equilibration of Ocean Tracers Software (FEOTS) is an end-to-end set of tools to efficiently calculate tracer distributions on a global or regional sub-domain using transport operators diagnosed from a comprehensive ocean model. To the best of our knowledge, this is the first application of a transport matrix model to an eddying ocean state. While a Newton–Krylov-based equilibration capability is still under development and not presented here, we demonstrate in this paper the transient modeling capabilities of FEOTS in an application focused on the Argentine Basin, where intense eddy activity and the Zapiola Anticyclone lead to strong mixing of water masses. The demonstration illustrates progress in developing offline passive tracer simulation capabilities, while highlighting the challenges of the impulse response functions approach in capturing tracer transports by a non-linear advection scheme. Our future work will focus on improving the computational efficiency of the code to reduce time-to-solution, using different basis functions to better represent non-linear advection operators, applying FEOTS to a parent model with unstructured grids (Ocean Model for Prediction Across Scales, MPAS-Ocean), and fully implementing a Newton–Krylov steady-state solver.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Load Margin Constrained Moving Target Defense against False Data Injection Attacks

Cyber physical security of power systems with high penetration of renewable generation has attracted attention from researchers. One critical issue is that cyber-physical attacks, disguised as uncertain renewable generation, can target conventional power system state estimation (SE). Moving target defense (MTD) is a promising defense strategy to detect stealthy false data injection (FDI) attacks against SE. However, all existing studies myopically perturb the reactance of transmission lines equipped with distributed flexible AC transmission system (D-FACTS) devices without adequately considering the system voltage stability. Exacerbated by the renewable generation uncertainty, existing MTD may cause voltage instability when the power grid is under stress. To address this issue, we propose a novel MTD framework that explicitly considers system voltage stability by using continuation power flow. We utilize the sensitivity matrix of power injection to line impedance, on which an optimization problem for maximizing load margin is formulated. This framework is validated on the IEEE 14-bus system and the IEEE 118-bus system, in which net load redistribution attacks are launched by sophisticated attackers. Steady-state simulations and dynamic simulations on PSS/E show the effectiveness of the proposed framework in circumventing the voltage instability while maintaining the detection effectiveness of MTD. The impact of the proposed method on attack detection effectiveness is also revealed.

Zhang, Hang↗
DOE OSTI2021

Mechanistic studies of NH 3 -assisted reduction of mononuclear Cu(ii) cation sites in Cu-CHA zeolites

Cu-Exchanged zeolites catalyze various redox reactions including the selective catalytic reduction (SCR) of NO x with NH 3 and the partial oxidation of hydrocarbons. The reduction of Cu(II) cations to Cu(I) by NH 3 alone has been observed experimentally, yet fundamental details regarding the Cu active site requirements, reaction stoichiometry, and reaction mechanism remain incompletely understood. Here, we synthesized model Cu-exchanged chabazite (Cu-CHA) zeolites with varying Cu ion densities and distributions of mononuclear Cu(II) ion site types (Cu 2+ , (CuOH) + ) and studied NH 3 -assisted Cu(II) reduction reactions using a combination of spectroscopic, titrimetric, and gas-phase product analysis methods. In situ UV-visible and X-ray absorption spectroscopies were used to monitor and quantify the transient reduction of Cu(II) to Cu(I) during exposure to NH 3 (473 K), in concert with titration methods that use NO and NH 3 co-reductants to fully reduce to the Cu(I) state any residual Cu(II) ions that remained after treatments in NH 3 alone for a given time period. The techniques provide quantitative evidence that both mononuclear Cu(II) site types are able to reduce in NH 3 alone, and do so to similar extents as a function of time. NH 3 temperature programmed reduction (TPR) revealed that the reaction stoichiometry of NH 3 -assisted reduction forms approximately one equivalent of N 2 per 6 Cu sites, regardless of Cu speciation or density, consistent with a six-electron reduction process whereby two NH 3 molecules react with six Cu(II) species to produce one N 2 molecule and six Cu(I) species. Furthermore, these findings provide new insights into the reaction pathways and mechanisms by which NH 3 alone reduces mononuclear Cu(II) sites in zeolites, which are undesired side-reactions that occur during steady-state NO x SCR and can unintentionally influence SCR-relevant spectroscopic or titrimetric characterization experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗