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All sources NASA NTRS DOE OSTI

DOE OSTI2025

Treyson Ricks - Intern Showcase Poster

Quinone-based sorbents offer a tunable, energy-efficient route to electrochemical CO2 capture, but systematic guidance for molecular design is lacking. Here, we report a high-throughput computational workflow that combines density functional theory (DFT) screening with machine-learning (ML) modeling to evaluate CO2 binding thermodynamics across several quinone derivatives, spanning benzoquinones, naphthoquinones, and anthraquinones. In addition to using solvents to stabilize the quinone anion and dianion, we studied the effect of ion-pairing on the reduction potentials and the CO2 binding energy. Automated Python scripts handled geometry optimizations and adduct-formation energies on an HPC cluster, reducing manual effort significantly. This integrated platform can uncover structure–property relationships and enables rapid in silico evaluation of untested candidates. We present one example from our workflow to showcase the capability of using quinones with ion-pairing to effectively capture CO2. Our approach paves the way for the rational selection of optimal quinone sorbents and can be extended with experimental thermochemical and kinetic data, alternative redox cycles, and stability assessments to accelerate development of next-generation electrochemical CO2 capture materials.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

NASA NTRS2001

Integral Twist Actuation of Helicopter Rotor Blades for Vibration Reduction

Active integral twist control for vibration reduction of helicopter rotors during forward flight is investigated. The twist deformation is obtained using embedded anisotropic piezocomposite actuators. An analytical framework is developed to examine integrally-twisted blades and their aeroelastic response during different flight conditions: frequency domain analysis for hover, and time domain analysis for forward flight. Both stem from the same three-dimensional electroelastic beam formulation with geometrical-exactness, and axe coupled with a finite-state dynamic inflow aerodynamics model. A prototype Active Twist Rotor blade was designed with this framework using Active Fiber Composites as the actuator. The ATR prototype blade was successfully tested under non-rotating conditions. Hover testing was conducted to evaluate structural integrity and dynamic response. In both conditions, a very good correlation was obtained against the analysis. Finally, a four-bladed ATR system is built and tested to demonstrate its concept in forward flight. This experiment was conducted at NASA Langley T~ansonic Dynamics Tunnel and represents the first-of-a-kind Mach-scaled fully-active-twist rotor system to undergo forward flight test. In parallel, the impact upon the fixed- and rotating-system loads is estimated by the analysis. While discrepancies are found in the amplitude of the loads under actuation, the predicted trend of load variation with respect to its control phase correlates well. It was also shown, both experimentally and numerically, that the ATR blade design has the potential for hub vibratory load reduction of up to 90% using individual blade control actuation. Using the numerical framework, system identification is performed to estimate the harmonic transfer functions. The linear time-periodic system can be represented by a linear time-invariant system under the three modes of blade actuation: collective, longitudinal cyclic, and lateral cyclic. A vibration minimizing controller is designed based on this result, which implements classical disturbance rejection algorithm with some modifications. The controller is simulated numerically, and more than 90% of the 4P hub vibratory load is eliminated. By accomplishing the experimental and analytical steps described in this thesis, the present concept is found to be a viable candidate for future generation low-vibration helicopters. Also, the analytical framework is shown to be very appropriate for exploring active blade designs, aeroelastic behavior prediction, and as simulation tool for closed-loop controllers.

Shin, SangJoon↗

DOE OSTI2022

Oxygen and Proton Transport in Flooded Graphene Pores with N-Dopants and Defects

Reactant transport is an important consideration in the design of ideal electrode structures. For the oxygen reduction reaction catalyzed by Pt/C in proton exchange membrane fuel cell cathodes, O 2 and H + delivery to Pt surfaces and H 2 O transport away are required. Some Pt nanoparticles may only be accessible via micropores that are too small for ionomer molecules to enter, possibly requiring flooding for H + transport. Here, to test if these “buried” Pt particles can play a role in activity through this proposed transport mechanism, we have performed atomic-scale simulations based on reactive force field molecular dynamics with an emphasis on confinement below 20 Å. Diffusion coefficients as a function of the molar concentration and local environment have been evaluated in water domains confined in two-dimensional graphene nanochannels of various channel heights representing a morphological model for micropores in proton exchange fuel cell cathodes. Our study shows that local atomic-scale structures can strongly modify H + , O 2 , and H 2 O transport rates in flooded micropores less than 20 Å in size. We find that there is a critical crossover in diffusion behavior around the 20 Å spacing with larger pores having bulk-like diffusion properties and confinement below 20 Å monotonically decreases diffusion rates. As pore size decreases, we observe locally dispersed water regions that ultimately strand reactants from long-distance transport. These findings suggest that flooded micropores may in fact be viable transport pathways for relevant reactants and products if the pore walls on opposite sides remain separated by ≥10 Å separation. Furthermore, the confinement effect is so strong that N-doping and C-vacancy defects in the C pore wall have only a minimal impact on diffusion rates and their effects are counterintuitively more apparent at larger spacings. These findings provide valuable insight regarding cathode performance and the role “stranded” catalyst particles may play in fuel cell cathodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1987

Experiments on reduction of propeller induced interior noise by active control of cylinder vibration

The feasibility of reducing interior noise caused by advanced turbo propellers by controlling the vibration of aircraft fuselages was investigated by performing experiments in an anechoic chamber with an aircraft model test rig and apparatus. It was found that active vibration control provides reasonable global attenuation of interior noise levels for the cases of resonant (at 576 Hz) and forced (at 708 Hz) system response. The controlling mechanism behind the effect is structural-acoustic coupling between the shell and the contained field, termed interface modal filtering.

Fuller, C. R.↗

DOE OSTI2015

Copper-Intercalated Birnessite as a Water Oxidation Catalyst

Here, we report a synthetic method to increase the catalytic activity of birnessite toward water oxidation by intercalating copper in the interlayer region of the layered manganese oxide. Intercalation of copper, verified by XRD, XPS, ICP, and Raman spectroscopy, was accomplished by exposing a suspension of birnessite to a Cu + -bearing precursor molecule that underwent disproportionation in solution to yield Cu 0 and Cu 2+ . Electrocatalytic studies reflected that the Cu-modified birnessite exhibited an overpotential for water oxidation of ~490 mV (at 10 mA/cm 2 ) and a Tafel slope of 126 mV/decade compared to ~700 mV (at 10 mA/cm 2 ) and 240 mV/decade, respectively, for birnessite without copper. Impedance spectroscopy results suggested that the charge transfer resistivity of the Cu-modified sample was significantly lower than Cu-free birnessite, suggesting that Cu in the interlayer increased the conductivity of birnessite leading to an enhancement of water oxidation kinetics. Density functional theory calculations show that the intercalation of Cu 0 into a layered MnO 2 model structure led to a change of the electronic properties of the material from a semiconductor to a metallic-like structure. This conclusion from computation is in general agreement with the aforementioned impedance spectroscopy results. X-ray photoelectron spectroscopy (XPS) showed that Cu 0 coexisted with Cu 2+ in the prepared Cu-modified birnessite. Control experiments using birnessite that was decorated with only Cu 2+ showed a reduction in water oxidation kinetics, further emphasizing the importance of Cu 0 for the increased activity of birnessite. The introduction of Cu 0 into the birnessite structure also increased the stability of the electrocatalyst. At a working current of 2 mA, the Cu-modified birnessite took ~3 times longer for the overpotential for water oxdiation to increase by 100 mV compared to when Cu was not present in the birnessite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2013

Arbitrary amplitude solitary and shock waves in an unmagnetized quantum dusty electron-positron-ion plasma

The behavior of quantum dust ion acoustic soliton and shocks in a plasma including inertialess quantum electrons and positrons, classical cold ions, and stationary negative dust grains are studied, using arbitrary amplitude approach. The effect of dissipation due to viscosity of ions is taken into account. The numerical analysis of Sagdeev potential for small value of quantum diffraction parameter (H) shows that for chosen plasma, only compressive solitons can exist and the existence domain of this type of solitons is decreased by increasing dust density (d). Additionally, the possibility of propagation of both subsonic and supersonic compressive solitons is investigated. It is shown that there is a critical dust density above which only supersonic solitons are observed. Moreover, increasing d leads to a reduction in the existence domain of compressive solitons and the possibility of propagation of rarefactive soliton is provided. So, rarefactive solitons are observed only due to the presence of dust particles in this model quantum plasma. Furthermore, numerical solution of governed equations for arbitrary amplitude shock waves has been investigated. It is shown that only compressive large amplitude shocks can propagate. Finally, the effects of plasma parameters on these structures are investigated. This research will be helpful in understanding the properties of dense astrophysical (i.e., white dwarfs and neutron stars) and laboratory dusty plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2016

Effect of dust charge fluctuations on dust acoustic structures in magnetized dusty plasma containing nonextensive electrons and two-temperature isothermal ions

Effect of dust electrical charge fluctuations on the nature of dust acoustic solitary waves (DASWs) in a four-species magnetized dusty plasma containing nonextensive electrons and two-temperature isothermal ions has been investigated. In this model, the negative dust electric charge is considered to be proportional to the plasma space potential. The nonlinear Zakharov–Kuznetsov (ZK) and modified Zakharov–Kuznetsov (mZK) equations are derived for DASWs by using the standard reductive perturbation method. The combined effects of electron nonextensivity and dust charge fluctuations on the DASW profile are analyzed. The different ranges of the nonextensive q-parameter are considered. The results show that solitary waves the amplitude and width of which depend sensitively on the nonextensive q-parameter can exist. Due to the electron nonextensivity and dust charge fluctuation rate, our dusty plasma model can admit both positive and negative potential solitons. The results show that the amplitude of the soliton increases with increasing electron nonextensivity, but its width decreases. Increasing the electrical charge fluctuations leads to a decrease in both the amplitude and width of DASWs.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2016

Report From BPTCS Project Team On Evaluation Of Additive Manufacturing For Pressure Retaining Equipment

ASME is evaluating the use of additive manufacturing (AM) for the construction of pressure equipment. The information in this report assesses available AM technologies for direct metal fabrication of pressure equipment. Background information is included in the report to provide context for those not experienced in AM technology. Only commercially available technologies for direct metal fabrication are addressed in the report because these AM methods are the only viable approaches for the construction of pressure equipment. Metal AM technologies can produce near-net shape parts by using multiple layers of material from a three dimensional (3D) design model of the geometry. Additive manufacturing of metal components was developed from polymer based rapid prototyping or 3D printing. At the current maturity level, AM application for pressure equipment has the potential to reduce delivery times and costs for complex shapes. AM will also lead to a reduction in the use of high cost materials, since parts can be created with corrosion resistant layers of high alloy material and structural layers of lower cost materials.

42 ENGINEERING↗

DOE OSTI2025

Uncovering Structure–Conductivity Relationships in Anion Exchange Membranes (AEMs) Using Interpretable Machine Learning

Anion exchange membranes (AEMs) play a vital role in the performance of water electrolyzers and fuel cells, yet their discovery and optimization remain challenging due to the complexity of structure–property relationships. In this study, we introduce a machine learning framework that leverages conditional graph neural networks (cGNNs) and descriptor-based models and a hybrid graph neural network (HGARE) to predict and interpret ionic conductivity. The descriptor-based pipeline employs principal component analysis (PCA), ablation, and SHAP analysis to identify factors governing anion conductivity, revealing electronic, topological, and compositional descriptors as key contributors. Beyond prediction, dimensionality reduction and clustering are performed by employing t-SNE and KMeans as well as SOM, which reveal distinct membranes clusters, some of which were enriched with high anion conductivity. Among graph-based approaches, the graph convolutional (GCN) achieved strong predictive performance, while the Hybrid Graph Autoencoder-Regressor Ensemble (HGARE) achieved the highest accuracy. Additionally, atom-level saliency maps from GCN provide spatial explanations for conductive behavior, revealing the importance of polarizable and flexible regions. This work contributes to the accelerated and data-driven design of high-performance AEMs.

Naghshnejad, Pegah [Department of Chemical Enginee↗

NASA NTRS1983

Waveform inversion of mantle Love waves: The born seismogram approach

Normal mode theory, extended to the slightly laterally heterogeneous Earth by the first-order Born approximation, is applied to the waveform inversion of mantle Love waves (200-500 sec) for the Earth's lateral heterogeneity at l=2 and a spherically symmetric anelasticity (Q sub mu) structure. The data are from the Global Digital Seismograph Network (GDSN). The l=2 pattern is very similar to the results of other studies that used either different methods, such as phase velocity measurements and multiplet location measurements, or a different data set, such as mantle Rayleigh waves from different instruments. The results are carefully analyzed for variance reduction and are most naturally explained by heterogeneity in the upper 420 km. Because of the poor resolution of the data set for the deep interior, however, a fairly large heterogeneity in the transition zones, of the order of up to 3.5% in shear wave velocity, is allowed. It is noteworthy that Love waves of this period range can not constrain the structure below 420 km and thus any model presented by similar studies below this depth are likely to be constrained by Rayleigh waves (spheroidal modes) only.

Tanimoto, T.↗

NASA NTRS1984

Forecast Impact of Components of the FGGE Observing System

Experiments have been conducted to assess the summer and winter forecast impact of the FGGE system, and of its main observing components: temperature sounding data derived from the TIROS-N polar orbiting satellite, cloud track winds determined from geostationary satellite observations and drifting buoy data which were collected by satellite during FGGE. The Analysis/Forecast System used has a number of improvements upon the system utilized by Halen et al. (1982) for the FGGE Special Observing Period-1 (SOP-1). Several modifications were made in the analysis scheme, the most important being the interpolation of the analysis minus 6 h forecast deviations rather than of the analyzed fields themselves. The forecast model is still the 4 deg lat, 5 deg lon and 9 vertical levels GLAS Fourth Order GCM with several minor corrections implemented in the physics and numerics. The improved vertical interpolation in the analysis resulted in better assimilation of rawinsonde data, which has more vertical structure than satellite data. As a result, there was an improvement of the forecasts derived from conventional data only, and, consequently, a small reduction of the positive impact of satellite data from that obtained by Halem et al. (1982).

Kalnay, E.↗

DOE OSTI2013

Quantifying the Sigma and Pi interactions between U(V) f orbitals and halide, alkyl, alkoxide, amide and ketimide ligands

f Orbital bonding in actinide and lanthanide complexes is critical to their behavior in a variety of areas from separations to magnetic properties. Octahedral f1 hexahalide complexes have been extensively used to study f orbital bonding due to their simple electronic structure and extensive spectroscopic characterization. The recent expansion of this family to include alkyl, alkoxide, amide, and ketimide ligands presents the opportunity to extend this study to a wider variety of ligands. To better understand f orbital bonding in these complexes, the existing molecular orbital (MO) model was refined to include the effect of covalency on spin orbit coupling in addition to its effect on orbital angular momentum (orbital reduction). The new MO model as well as the existing MO model and the crystal field (CF) model were applied to the octahedral f1 complexes to determine the covalency and strengths of the ? and ? bonds formed by the f orbitals. When covalency is significant, MO models more precisely determined the strengths of the bonds derived from the f orbitals; however, when covalency was small, the CF model was better than either MO model. The covalency determined using the new MO model is in better agreement with both experiment and theory than that predicted by the existing MO model. The results emphasize the role played by the orbital energy in determining the strength and covalency of bonds formed by the f orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Dependence of spin pumping and spin transfer torque upon Ni 81 Fe 19 thickness in Ta / Ag / Ni 81 Fe 19 / Ag / Co 2 MnGe / Ag / Ta spin-valve structures

Spin pumping has been studied within Ta / Ag / Ni 81 Fe 19 (0–5 nm) / Ag (6 nm) / Co 2 MnGe (5 nm) / Ag / Ta large-area spin-valve structures, and the transverse spin current absorption of Ni 81 Fe 19 sink layers of different thicknesses has been explored. In some circumstances, the spin current absorption can be inferred from the modification of the Co 2 MnGe source layer damping in vector network analyzer ferromagnetic resonance (VNA-FMR) experiments. However, the spin current absorption is more accurately determined from element-specific phase-resolved x-ray ferromagnetic resonance (XFMR) measurements that directly probe the spin transfer torque (STT) acting on the sink layer at the source layer resonance. Comparison with a macrospin model allows the real part of the effective spin mixing conductance to be extracted. We find that spin current absorption in the outer Ta layers has a significant impact, while sink layers with thicknesses of less than 0.6 nm are found to be discontinuous and superparamagnetic at room temperature, and lead to a noticeable increase of the source layer damping. For the thickest 5-nm sink layer, increased spin current absorption is found to coincide with a reduction of the zero frequency FMR linewidth that we attribute to improved interface quality. Furthermore, this study shows that the transverse spin current absorption does not follow a universal dependence upon sink layer thickness but instead the structural quality of the sink layer plays a crucial role.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2019

COMBUSTION AND EMISSION CHARACTERISTICS OF A LEAN AXIAL-STAGE COMBUSTOR

Gas turbine engines with high operational flexibility represent an important area of research. In support of this, the reduction of NOx emissions at high-temperature, full-load conditions are the main target of this research study. To overcome the challenge of decreasing the residence time of hot exhaust gas in the burner, the approach of axial-staged combustion has been used, which aims to burn at lean conditions. A main combustion stage with a conventional burner is followed by a jet-in-crossflow (JIC) stage downstream. This second combustion stage, the test section, burns well over a third of the total fuel amount, which is added by a jet inlet. A steady Computational Fluid Dynamics (CFD) model in Star-CCM+ was created to analyze the JIC stage. A structured mesh grid with 1.7 million cells and local refinement domains was used along with RANS equations, Realizable k-ε turbulence, Complex Chemistry model with Laminar Flame Concept (LFC) applied. The findings of the computational model include a detailed description of the flow field, focusing on vortex formation and penetration depth. Three vortex types and local pressure losses of up to 6% in the mixing domain were identified. Results were compared with similar data from literature and a very good match was yielded. Optical laser diagnostics should work well to capture the predicted flow penetration. The highest local reaction rates were observed inside a thin flame front, 4 to 6 diameters downstream of the jet. The jet showed a limited expansion into the available channel domain, resulting in low heat release and a methane conversion of only 52%. Providing an enhanced amount of oxygen was proven to increase the CH4 conversion significantly. Emissions were analyzed for an estimated species composition from the main burner. A CO production of 9.85‰ and the reduction of an incoming NOx amount by 15% were determined, outlining the potential of axial-staged combustion. Further numerical investigation along with experimental verification is in progress.

03 NATURAL GAS↗

DOE OSTI2018

GPU Data Access on Complex Geometries for D3Q19 Lattice Boltzmann Method

GPU performance of the lattice Boltzmann method (LBM) depends heavily on memory access patterns. When LBM is advanced with GPUs on complex computational domains, geometric data is typically accessed indirectly, and lattice data is typically accessed lexicographically in the Structure of Array (SoA) layout. Although there are a variety of existing access patterns beyond the typical choices, no study has yet examined the relative efficacy between them. Here, we compare a suite of memory access schemes via empirical testing and performance modeling. We find strong evidence that semi-direct addressing is the superior addressing scheme for the majority of cases examined: Semi-direct addressing increases computational speed and often reduces memory consumption. For lattice layout, we find that the Collected Structure of Arrays (CSoA) layout outperforms the SoA layout. When compared to state-of-the-art practices, our recommended addressing modifications lead to performance gains between 10-40% across different complex geometries, fluid volume fractions, and resolutions. The modifications also lead to a decrease in memory consumption by as much as 17%. Having discovered these improvements, we examine a highly resolved arterial geometry on a leadership class system. On this system we present the first near-optimal strong results for LBM with arterial geometries run on GPUs. We also demonstrate that the above recommendations remain valid for large scale, many device simulations, which leads to an increased computational speed and average memory usage reductions. To understand these observations, we employ performance modeling which reveals that semi-direct methods outperform indirect methods due to a reduced number of total loads/stores in memory, and that CSoA outperforms SoA and bundling due to improved caching behavior.

Herschlag, Gregory↗

DOE OSTI2019

Reduction-dependent siderophore assimilation in a model pennate diatom

Significance Diatoms can access inorganic iron with remarkable efficiency, but this process is contingent on carbonate ion concentration. As ocean acidification reduces carbonate concentration, inorganic iron uptake may be discouraged in favor of carbonate-independent uptake. We report details of an iron assimilation process that needs no carbonate but requires exogenous compounds produced by cooccurring organisms. We show this process to be critical for diatom growth at high siderophore concentrations, but ineffective at acquiring iron from low-affinity organic chelators or lithogenic particulates. Understanding the caveats associated with iron source preference in diatoms will help predict the impacts of climate change on microbial community structure in high-nitrate low-chlorophyll ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2017

Zero-Boil-Off Tank (ZBOT) Experiment: Ground-Based Validation of Self-Pressurization and Pressure Control Two-Phase CFD Model

Integral to all phases of NASA's projected space and planetary expeditions is affordable and reliable cryogenic fluid storage for use in propellant or life support systems. Cryogen vaporization due to heat leaks into the tank from its surroundings and support structure can cause self-pressurization relieved through venting. This has led to a desire to develop innovative pressure control designs based on mixing of the bulk tank fluid together with some form of active or passive cooling to allow storage of the cryogenic fluid with zero or reduced boil-off. The Zero-Boil-Off Tank (ZBOT) Experiments are a series of small scale tank pressurization and pressure control experiments aboard the International Space Station (ISS) that use a transparent volatile simulant fluid in a transparent sealed tank to delineate various fundamental fluid flow, heat and mass transport, and phase change phenomena that control storage tank pressurization and pressure control in microgravity. The hardware for ZBOT-1 flew to ISS on the OA-7 flight in April 2017 and operations are planned to begin in September 2017, encompassing more than 90 tests. This paper presents preliminary results from ZBOT's ground-based research delineating both pressurization and pressure reduction trends in the sealed test tank. Tank self-pressurization tests are conducted under three modes: VJ heating, strip heating and simultaneous VJ and strip heating in attempt to simulate heat leaks from the environment, the support structure and both. The jet mixing pressure control studies are performed either from an elevated uniform temperature condition or from thermally stratified conditions following a self-pressurization run. Jet flow rates are varied from 2-25 cm/s spanning a range of jet Re number in laminar, transitional, and turbulent regimes and a range of Weber numbers covering no ullage penetration, partial penetration and complete ullage penetration and break-up (only in microgravity). Numerical prediction of a two-phase CFD model are compared to experimental 1g results to both validate the model and also indicate the effect of the residual non-condensable gas on evolution of pressure and temperature distributions in the tank during pressurization and pressure control.

microgravity evaporation condensatio↗

DOE OSTI2025

Nitrate-To-Ammonia Electroconversion at Neutral pH on Polycrystalline Vanadium Sulfide Derived from Vanadium Disulfide

The electrochemical nitrate reduction reaction (NO3RR) offers a pathway to produce NH3 for fuel and fertilizer from waste NO3-. In this work, a polycrystalline vanadium sulfide (VSx), which is derived from solvothermally grown and annealed VS2, is shown to exhibit excellent NO3RR activity (2.3 +- 0.6 mg.cm-2 geo..h-1 @ -0.92 VRHE) and Faradaic efficiency to NH4+ (69 +- 6% at -0.69 VRHE) in buffered neutral pH electrolyte containing 0.1 M NO3-. A variety of characterization techniques are leveraged to support the VSx assignment, including X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, selected area electron diffraction, and X-ray diffraction measurements. The VS2 annealing step reduces the oxide character and generates VSx, which, based on the improved NO3RR activity, results in the creation of active sites for NO3- binding. To help shed light on NO3RR on VSx, VS2 is used as a model system, and a grand-canonical density functional theory (GC-DFT) investigation of VS2 shows strong evidence that S vacancies are active sites for NO3RR, where NO3- outcompetes H+ for adsorption at the S-vacancy sites. Moreover, GC-DFT results highlight a thermodynamically favorable reaction to generate NH4+ in an aqueous electrolyte at relevant cathodic potentials. As an annealed material, VSx may contain undersaturated V sites, which show an electronic structure similar to the theoretically calculated S-vacancy site of VS2, and these sites may contribute to the observed increase in NO3RR activity and selectivity for NH4+ on VSx versus unannealed VS2. Finally, kinetic isotope effect measurements suggest that the kinetic rate-limiting step of the NO3RR on VSx is not proton-coupled, indicating it may be the first electron transfer to adsorbed NO3*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗