Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “sequential experiment”

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

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

At least 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Numerical coupling of aerosol emissions, dry removal, and turbulent mixing in the E3SM Atmosphere Model version 1 (EAMv1) – Part 1: Dust budget analyses and the impacts of a revised coupling scheme

Abstract. An earlier study evaluating dust life cycle in the Energy Exascale Earth System Model (E3SM) Atmosphere Model version 1 (EAMv1) has revealed that the simulated global mean dust lifetime is substantially shorter when higher vertical resolution is used, primarily due to significant strengthening of dust dry removal in source regions. This paper demonstrates that the sequential splitting of aerosol emissions, dry removal, and turbulent mixing in the model's time integration loop, especially the calculation of dry removal after surface emissions and before turbulent mixing, is the primary reason for the vertical resolution sensitivity reported in that earlier study. Based on this reasoning, we propose a revised numerical process coupling scheme that requires the least amount of code changes, in which the surface emissions are applied before turbulent mixing instead of before dry removal. The revised scheme allows newly emitted particles to be transported aloft by turbulence before being removed from the atmosphere, and hence better resembles the dust life cycle in the real world. Sensitivity experiments show that the revised process coupling substantially weakens dry removal and strengthens vertical mixing in dust source regions. It also strengthens the large-scale transport from source to non-source regions, strengthens dry removal outside the source regions, and strengthens wet removal and activation globally. In transient simulations of the years 2000–2009 conducted using 1∘ horizontal grid spacing, 72 vertical layers, and unchanged tuning parameters of emission strength, the revised process coupling leads to a 40 % increase in the global total dust burden and an increase of dust lifetime from 1.8 to 2.5 d in terms of 10-year averages. Weakened dry removal and increased mixing ratios are also seen for other aerosol species that have substantial surface emissions, although the changes in mixing ratio are considerably smaller for the submicron species than for dust and sea salt. Numerical experiments confirm that the revised coupling scheme significantly reduces the strong and non-physical sensitivities of model results to vertical resolution in the original EAMv1. This provides a motivation for adopting the revised scheme in EAM as well as for further improvements on the simple revision presented in this paper.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2010

Current Trends in Satellite Laser Ranging

Satellite Laser Ranging (SLR) techniques are used to accurately measure the distance from ground stations to retroreflectors on satellites and the moon. SLR is one of the fundamental techniques that define the international Terrestrial Reference Frame (iTRF), which is the basis upon which we measure many aspects of global change over space, time, and evolving technology. It is one of the fundamental techniques that define at a level of precision of a few mm the origin and scale of the ITRF. Laser Ranging provides precision orbit determination and instrument calibration/validation for satellite-borne altimeters for the better understanding of sea level change, ocean dynamics, ice budget, and terrestrial topography. Laser ranging is also a tool to study the dynamics of the Moon and fundamental constants. Many of the GNSS satellites now carry retro-reflectors for improved orbit determination, harmonization of reference frames, and in-orbit co-location and system performance validation. The GNSS Constellations will be the means of making the reference frame available to worldwide users. Data and products from these measurements support key aspects of the GEOSS 10-Year implementation Plan adopted on February 16, 2005, The ITRF has been identified as a key contribution of the JAG to GEOSS and the ILRS makes a major contribution for its development since its foundation. The ILRS delivers weekly additional realizations that are accumulated sequentially to extend the ITRF and the Earth Orientation Parameter (EOP) series with a daily resolution. Additional products are currently under development such as precise orbits of satellites, EOP with daily availability, low-degree gravitational harmonics for studies of Earth dynamics and kinematics, etc. SLR technology continues to evolve toward the next generation laser ranging systems as programmatic requirements become more stringent. Ranging accuracy is improving as higher repetition rate, narrower pulse lasers and faster detectors are implemented. Automation and pass interleaving at some stations is already expanding temporal coverage. Web-based safety keys are allowing the SLR network stations to range to optically vulnerable satellites. Some stations are experimenting with two-wavelength operation as a means of better understanding the atmospheric refraction and with very low power laser to improve eye-safety conditions. New retroreflector designs are improving the signal link and enable daylight ranging. Dramatic improvements have also been made with lunar ranging with the new APOLLO Site in New ?Mexico, USA and the upgraded lunar station "MEO" in Grasse,

Pearlman, M. R.↗
NASA NTRS1997

Tracking of Ice Edges and Ice Floes by Wavelet Analysis of SAR Images

This paper demonstrates the use of wavelet transforms in the tracking of sequential ice features in the ERS-1 synthetic aperture radar (SAR) imagery, especially in situations where feature correlation techniques fail to yield reasonable results. Examples include the evolution of the St. Lawrence polynya and summer sea ice change in the Beaufort Sea. For the polynya, the evolution of the region of young ice growth surrounding a polynya can be easily tracked by wavelet analysis due to the large backscatter difference between the young and old ice. Also within the polynya, a 2D fast Fourier transform (FFT) is used to identify the extent of the Langmuir circulation region, which is coincident with the wave-agitated frazil ice growth region, where the sea ice experiences its fastest growth. Therefore, the combination of wavelet and FFT analysis of SAR images provides for the large-scale monitoring of different polynya features. For summer ice, previous work shows that this is the most difficult period for ice trackers due to the lack of features on the sea ice cover. The multiscale wavelet analysis shows that this method delineates the detailed floe shapes during this period, so that between consecutive images, the floe translation and rotation can be estimated.

Liu, Antony K.↗
NASA NTRS2011

Binomial Test Method for Determining Probability of Detection Capability for Fracture Critical Applications

The capability of an inspection system is established by applications of various methodologies to determine the probability of detection (POD). One accepted metric of an adequate inspection system is that for a minimum flaw size and all greater flaw sizes, there is 0.90 probability of detection with 95% confidence (90/95 POD). Directed design of experiments for probability of detection (DOEPOD) has been developed to provide an efficient and accurate methodology that yields estimates of POD and confidence bounds for both Hit-Miss or signal amplitude testing, where signal amplitudes are reduced to Hit-Miss by using a signal threshold Directed DOEPOD uses a nonparametric approach for the analysis or inspection data that does require any assumptions about the particular functional form of a POD function. The DOEPOD procedure identifies, for a given sample set whether or not the minimum requirement of 0.90 probability of detection with 95% confidence is demonstrated for a minimum flaw size and for all greater flaw sizes (90/95 POD). The DOEPOD procedures are sequentially executed in order to minimize the number of samples needed to demonstrate that there is a 90/95 POD lower confidence bound at a given flaw size and that the POD is monotonic for flaw sizes exceeding that 90/95 POD flaw size. The conservativeness of the DOEPOD methodology results is discussed. Validated guidelines for binomial estimation of POD for fracture critical inspection are established.

Generazio, Edward R.↗
NASA NTRS1998

In-Flight System Identification

A method is proposed and studied whereby the system identification cycle consisting of experiment design and data analysis can be repeatedly implemented aboard a test aircraft in real time. This adaptive in-flight system identification scheme has many advantages, including increased flight test efficiency, adaptability to dynamic characteristics that are imperfectly known a priori, in-flight improvement of data quality through iterative input design, and immediate feedback of the quality of flight test results. The technique uses equation error in the frequency domain with a recursive Fourier transform for the real time data analysis, and simple design methods employing square wave input forms to design the test inputs in flight. Simulation examples are used to demonstrate that the technique produces increasingly accurate model parameter estimates resulting from sequentially designed and implemented flight test maneuvers. The method has reasonable computational requirements, and could be implemented aboard an aircraft in real time.

Morelli, Eugene A.↗
NASA NTRS2004

Multivariate Error Covariance Estimates by Monte-Carlo Simulation for Assimilation Studies in the Pacific Ocean

One of the most difficult aspects of ocean state estimation is the prescription of the model forecast error covariances. The paucity of ocean observations limits our ability to estimate the covariance structures from model-observation differences. In most practical applications, simple covariances are usually prescribed. Rarely are cross-covariances between different model variables used. Here a comparison is made between a univariate Optimal Interpolation (UOI) scheme and a multivariate OI algorithm (MvOI) in the assimilation of ocean temperature. In the UOI case only temperature is updated using a Gaussian covariance function and in the MvOI salinity, zonal and meridional velocities as well as temperature, are updated using an empirically estimated multivariate covariance matrix. Earlier studies have shown that a univariate OI has a detrimental effect on the salinity and velocity fields of the model. Apparently, in a sequential framework it is important to analyze temperature and salinity together. For the MvOI an estimation of the model error statistics is made by Monte-Carlo techniques from an ensemble of model integrations. An important advantage of using an ensemble of ocean states is that it provides a natural way to estimate cross-covariances between the fields of different physical variables constituting the model state vector, at the same time incorporating the model's dynamical and thermodynamical constraints as well as the effects of physical boundaries. Only temperature observations from the Tropical Atmosphere-Ocean array have been assimilated in this study. In order to investigate the efficacy of the multivariate scheme two data assimilation experiments are validated with a large independent set of recently published subsurface observations of salinity, zonal velocity and temperature. For reference, a third control run with no data assimilation is used to check how the data assimilation affects systematic model errors. While the performance of the UOI and MvOI is similar with respect to the temperature field, the salinity and velocity fields are greatly improved when multivariate correction is used, as evident from the analyses of the rms differences of these fields and independent observations. The MvOI assimilation is found to improve upon the control run in generating the water masses with properties close to the observed, while the UOI failed to maintain the temperature and salinity structure.

Borovikov, Anna↗
NASA NTRS1994

Improved solution accuracy for TDRSS-based TOPEX/Poseidon orbit determination

Orbit determination results are obtained by the Goddard Space Flight Center (GSFC) Flight Dynamics Division (FDD) using a batch-least-squares estimator available in the Goddard Trajectory Determination System (GTDS) and an extended Kalman filter estimation system to process Tracking and Data Relay Satellite (TDRS) System (TDRSS) measurements. GTDS is the operational orbit determination system used by the FDD in support of the Ocean Topography Experiment (TOPEX)/Poseidon spacecraft navigation and health and safety operations. The extended Kalman filter was implemented in an orbit determination analysis prototype system, closely related to the Real-Time Orbit Determination System/Enhanced (RTOD/E) system. In addition, the Precision Orbit Determination (POD) team within the GSFC Space Geodesy Branch generated an independent set of high-accuracy trajectories to support the TOPEX/Poseidon scientific data. These latter solutions use the geodynamics (GEODYN) orbit determination system with laser ranging and Doppler Orbitography and Radiopositioning integrated by satellite (DORIS) tracking measurements. The TOPEX/Poseidon trajectories were estimated for November 7 through November 11, 1992, the timeframe under study. Independent assessments were made of the consistencies of solutions produced by the batch and sequential methods. The batch-least-squares solutions were assessed based on the solution residuals, while the sequential solutions were assessed based on primarily the estimated covariances. The batch-least-squares and sequential orbit solutions were compared with the definitive POD orbit solutions. The solution differences were generally less than 2 meters for the batch-least-squares and less than 13 meters for the sequential estimation solutions. After the sequential estimation solutions were processed with a smoother algorithm, position differences with POD orbit solutions of less than 7 meters were obtained. The differences among the POD, GTDS, and filter/smoother solutions can be traced to differences in modeling and tracking data types, which are being analyzed in detail.

Doll, C. E.↗
NASA NTRS1998

Effect of Apex Flap Deflection on Vertical Tail Buffeting

A computational study of the effect of vortex breakdown location on vertical tail buffeting is conducted. The position of the breakdown is modified by employing an apex flap deflected by an experimentally determined optimal angle. The delayed breakdown flow and buffeting response is then compared to the nominal undeflected case. This multidisciplinary problem is solved sequentially for the fluid flow, the elastic tail deformations and the grid displacements. The fluid flow is simulated by time accurately solving the unsteady, compressible, Reynolds-averaged Navier-Stokes equations using an implicit, upwind, flux-difference splitting finite volume scheme. The elastic vibrations of the tails are modeled by uncoupled bending and torsion beam equations. These equations are solved accurately in time using the Galerkin method and a five-stage Runge-Kutta-Verner scheme. The grid for the fluid dynamics calculations is continuously deformed using interpolation functions to disperse the displacements smoothly throughout the computational domain. An angle-of-attack of 35 deg.is chosen such that the wing primary-vortex cores experience vortex breakdown and the resulting turbulent wake flow impinges on tile vertical tails. The dimensions and material properties of the vertical tails are chosen such that the deflections are large enough to insure interaction with the flow, and the natural frequencies are high enough to facilitate a practical computational solution. Results are presented for a baseline uncontrolled buffeting case and a delayed breakdown case in which the apex flap has been deflected 15 deg. The flap was found to be very effective in delaying the breakdown, increasing the location from 50%c to 94%c, which resulted in a 6% increase in lift coefficient and pitching moment. However, the integrated buffet loads and tip responses were roughly equivalent for the two cases.

Massey, Steven J.↗
NASA NTRS2010

Multiple Velocity Profile Measurements in Hypersonic Flows using Sequentially-Imaged Fluorescence Tagging

Nitric-oxide planar laser-induced fluorescence (NO PLIF) was used to perform velocity measurements in hypersonic flows by generating multiple tagged lines which fluoresce as they convect downstream. For each laser pulse, a single interline, progressive scan intensified CCD camera was used to obtain separate images of the initial undelayed and delayed NO molecules that had been tagged by the laser. The CCD configuration allowed for sub-microsecond acquisition of both images, resulting in sub-microsecond temporal resolution as well as sub-mm spatial resolution (0.5-mm x 0.7-mm). Determination of axial velocity was made by application of a cross-correlation analysis of the horizontal shift of individual tagged lines. Quantification of systematic errors, the contribution of gating/exposure duration errors, and influence of collision rate on fluorescence to temporal uncertainty were made. Quantification of the spatial uncertainty depended upon the analysis technique and signal-to-noise of the acquired profiles. This investigation focused on two hypersonic flow experiments: (1) a reaction control system (RCS) jet on an Orion Crew Exploration Vehicle (CEV) wind tunnel model and (2) a 10-degree half-angle wedge containing a 2-mm tall, 4-mm wide cylindrical boundary layer trip. The experiments were performed at the NASA Langley Research Center's 31-inch Mach 10 wind tunnel.

Bathel, Brett F.↗
NASA NTRS1993

Comparison of TOPEX/Poseidon orbit determination solutions obtained by the Goddard Space Flight Center Flight Dynamics Division and Precision Orbit Determination Teams

Orbit determination results are obtained by the Goddard Space Flight Center (GSFC) Flight Dynamics Division (FDD) using the Goddard Trajectory Determination System (GTDS) and a real-time extended Kalman filter estimation system to process Tracking Data and Relay Satellite (TDRS) System (TDRSS) measurements in support of the Ocean Topography Experiment (TOPEX)/Poseidon spacecraft navigation and health and safety operations. GTDS is the operational orbit determination system used by the FDD, and the extended Kalman fliter was implemented in an analysis prototype system, the Real-Time Orbit Determination System/Enhanced (RTOD/E). The Precision Orbit Determination (POD) team within the GSFC Space Geodesy Branch generates an independent set of high-accuracy trajectories to support the TOPEX/Poseidon scientific data. These latter solutions use the Geodynamics (GEODYN) orbit determination system with laser ranging tracking data. The TOPEX/Poseidon trajectories were estimated for the October 22 - November 1, 1992, timeframe, for which the latest preliminary POD results were available. Independent assessments were made of the consistencies of solutions produced by the batch and sequential methods. The batch cases were assessed using overlap comparisons, while the sequential cases were assessed with covariances and the first measurement residuals. The batch least-squares and forward-filtered RTOD/E orbit solutions were compared with the definitive POD orbit solutions. The solution differences were generally less than 10 meters (m) for the batch least squares and less than 18 m for the sequential estimation solutions. The differences among the POD, GTDS, and RTOD/E solutions can be traced to differences in modeling and tracking data types, which are being analyzed in detail.

Doll, C.↗
NASA NTRS2018

Dynamic Adjustment of Simulation Parameters for Efficient Vehicle Prognostics

Model-based diagnostics and prognostics rely on state estimation and uncertainty management algorithms to produce useful information for system operators and maintainers. This information enables more informed operational decisions, condition-based maintenance, and overall mission safety assurance. Typically, uncertainty is associated with vehicle state-of-health estimation and prediction results because of modeling errors, internal or external sources of noise, and sensor inaccuracy. Probabilistic uncertainty management methods including Sequential Monte Carlo simulation are commonly used to reason about state-of-health estimates and predictions in the presence of these sources of uncertainty. However, such algorithms can be computationally expensive as they require a very large number of samples to obtain a sufficiently accurate quantification of the end of life probability distribution. As a result, highly mobile autonomous systems that leverage the prognostic results for mission-level replanning are often constrained in their processing capability because of these computationally expensive simulation approaches. Therefore, in this paper, we investigate algorithmic methods for dynamically adjusting simulation time step as well as number of samples to achieve highly efficient prognostic results while maintaining results accuracy. Results obtained from simulated flight experiments of an electric unmanned aerial vehicle are presented to verify the efficacy of such algorithms.

Prognostics↗
DOE OSTI2021

Genome, transcriptome and secretome analyses of the antagonistic, yeast-like fungus Aureobasidium pullulans to identify potential biocontrol genes

Aureobasidium pullulans is an extremotolerant, cosmopolitan yeast-like fungus that successfully colonises vastly different ecological niches. The species is widely used in biotechnology and successfully applied as a commercial biocontrol agent against postharvest diseases and fireblight. However, the exact mechanisms that are responsible for its antagonistic activity against diverse plant pathogens are not known at the molecular level. Thus, it is difficult to optimise and improve the biocontrol applications of this species. As a foundation for elucidating biocontrol mechanisms, we have de novo assembled a high-quality reference genome of a strongly antagonistic A. pullulans strain, performed dual RNA-seq experiments, and analysed proteins secreted during the interaction with the plant pathogen Fusarium oxysporum. Based on the genome annotation, potential biocontrol genes were predicted to encode secreted hydrolases or to be part of secondary metabolite clusters (e.g., NRPS-like, NRPS, T1PKS, terpene, and β-lactone clusters). Transcriptome and secretome analyses defined a subset of 79 A. pullulans genes (among the 10,925 annotated genes) that were transcriptionally upregulated or exclusively detected at the protein level during the competition with F. oxysporum. These potential biocontrol genes comprised predicted secreted hydrolases such as glycosylases, esterases, and proteases, as well as genes encoding enzymes, which are predicted to be involved in the synthesis of secondary metabolites. This study highlights the value of a sequential approach starting with genome mining and consecutive transcriptome and secretome analyses in order to identify a limited number of potential target genes for detailed, functional analyses.

transcriptome↗
NASA NTRS1979

Mapping of sea ice and measurement of its drift using aircraft synthetic aperture radar images

Side-looking radar images of Arctic sea ice were obtained as part of the Arctic Ice Dynamics Joint Experiment. Repetitive coverages of a test site in the Arctic were used to measure sea ice drift, employing single images and blocks of overlapping radar image strips; the images were used in conjunction with data from the aircraft inertial navigation and altimeter. Also, independently measured, accurate positions of a number of ground control points were available. Initial tests of the method were carried out with repeated coverages of a land area on the Alaska coast (Prudhoe). Absolute accuracies achieved were essentially limited by the accuracy of the inertial navigation data. Errors of drift measurements were found to be about + or - 2.5 km. Relative accuracy is higher; its limits are set by the radar image geometry and the definition of identical features in sequential images. The drift of adjacent ice features with respect to one another could be determined with errors of less than + or - 0.2 km.

Leberl, F.↗
NASA NTRS1982

Observational constraints for a theoretical model describing the soft X-ray flare

High-resolution solar flare X-ray spectra have recently been obtained from X-ray spectrometer experiments flown on an Air Force spacecraft (P78-1) launched on 1979 February 24. Interpretation of the spectra has produced new results concerning the physical conditions and time behavior of the thermal soft X-ray emitting plasma at temperatures near 20,000,000 K. It is argued that soft and hard X-ray events are not causally related to each other, but are simply two different manifestations of flare energy release. They probably occur in different plasma volumes. The source of the preflare plasma appears to be in the cooler parts of the solar atmosphere, perhaps transition region loops with initial temperatures of 100,000 K and densities of 10 to the 11th per cu cm. Continuous energy input, rather than sequential activation of loops, is required to explain the observations. Compression coupled with chromospheric ablation may produce the high densities in coronal flare loops.

Feldman, U.↗
NASA NTRS1981

Human factors in equipment development for the Space Shuttle - A study of the general purpose work station

The results of a human factors test to assay the suitability of a prototype general purpose work station (GPWS) for biosciences experiments on the fourth Spacelab mission are reported. The evaluation was performed to verify that users of the GPWS would optimally interact with the GPWS configuration and instrumentation. Six male subjects sat on stools positioned to allow assimilation of the zero-g body posture. Trials were run concerning the operator viewing angles facing the console, the console color, procedures for injecting rates with dye, a rat blood cell count, mouse dissection, squirrel monkey transfer, and plant fixation. The trials were run for several days in order to gage improvement or poor performance conditions. Better access to the work surface was found necessary, together with more distinct and better located LEDs, better access window latches, clearer sequences on control buttons, color-coded sequential buttons, and provisions made for an intercom system when operators of the GPWS work in tandem.

Junge, M. K.↗
DOE OSTI2022

Curriculum-based Reinforcement Learning for Distribution System Critical Load Restoration

This paper focuses on the critical load restoration problem in distribution systems following major outages. To provide fast online response and optimal sequential decision-making support, a reinforcement learning (RL) based approach is proposed to optimize the restoration. Due to the complexities stemming from the large policy search space, renewable uncertainty, and nonlinearity in a complex grid control problem, directly applying RL algorithms to train a satisfactory policy requires extensive tuning to be successful. To address this challenge, this paper leverages the curriculum learning (CL) technique to design a training curriculum involving a simpler steppingstone problem that guides the RL agent to learn to solve the original hard problem in a progressive and more effective manner. We demonstrate that compared with direct learning, CL facilitates controller training to achieve better performance. To study realistic scenarios where renewable forecasts used for decision-making are in general imperfect, the experiments compare the trained RL controllers against two model predictive controllers (MPCs) using renewable forecasts with different error levels and observe how these controllers can hedge against the uncertainty. Results show that RL controllers are less susceptible to forecast errors than the baseline MPCs and can provide a more reliable restoration process.

24 POWER TRANSMISSION AND DISTRIBUTION↗
NASA NTRS1990

Motion detection in astronomical and ice floe images

Two approaches are presented for establishing correspondence between small areas in pairs of successive images for motion detection. The first one, based on local correlation, is used on a pair of successive Voyager images of the Jupiter which differ mainly in locally variable translations. This algorithm is implemented on a sequential machine (VAX 780) as well as the Massively Parallel Processor (MPP). In the case of the sequential algorithm, the pixel correspondence or match is computed on a sparse grid of points using nonoverlapping windows (typically 11 x 11) by local correlations over a predetermined search area. The displacement of the corresponding pixels in the two images is called the disparities to cubic surfaces. The disparities at points where the error between the computed values and the surface values exceeds a particular threshold are replaced by the surface values. A bilinear interpolation is then used to estimate disparities at all other pixels between the grid points. When this algorithm was applied at the red spot in the Jupiter image, the rotating velocity field of the storm was determined. The second method of motion detection is applicable to pairs of images in which corresponding areas can experience considerable translation as well as rotation.

Manohar, M.↗
DOE OSTI2022

Thermal Hydroquinone Oxidation on Co/N-doped Carbon Proceeds by a Band-Mediated Electrochemical Mechanism

Molecules catalyze aerobic oxidation reactions via redox cycling at the metal center to effect sequential activation of O 2 and the substrate. Metal surfaces can catalyze the same transformations by coupling independent half-reactions for oxygen reduction and substrate oxidation mediated via the exchange of band-electrons. Metal/nitrogen-doped carbons (MNCs) are promising catalysts for aerobic oxidation that consist of molecule-like active sites embedded in a conductive carbon host. Owing to their combining molecular and metallic features, it remains unclear whether they proceed via the sequential redox cycling pathways of molecules or the band-mediated pathways of metals. Herein, we simultaneously track the potential of the catalyst and the rate of the turnover of aerobic hydroquinone oxidation on a cobalt-based MNC catalyst contacted to a catalytically inactive carbon electrode. By comparing operando measurements of rate and potential with the current-voltage behavior of each constituent half-reaction under identical conditions, we show that these molecular materials can display the band-mediated reaction mechanisms of extended metallic solids. Further, we show that the action of these band-mediated mechanisms explains fractional reaction orders in both oxygen and hydroquinone, the time evolution of catalyst potential and rate, and the dependence of rate on overall reaction free energy. Selective poisoning experiments suggest that oxygen reduction proceeds at cobalt sites, whereas quinone oxidation proceeds at native oxidic defects on the carbon. These findings highlight that molecule-like active sites can take advantage of band-mediated mechanisms when coupled to conductive hosts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗